bluuebunny/crossref_metadata_2025 huggingface dataset:
Freshwater wetland plants respond nonlinearly to inundation over a sustained period
Authors: Zhao Junbin , Malone Sparkle L. , Staudhammer Christina L. , Starr Gregory , Hartmann Henrik , Oberbauer Steven F.
Published: October 2021

Premise

Wetland plants regularly experience physiological stresses resulting from inundation; however, plant responses to the interacting effects of water level and inundation duration are not fully understood.

Methods

We conducted a mesocosm experiment on two wetland species, sawgrass (Cladium jamaicense) and muhly grass (Muhlenbergia filipes), that co‐dominate many freshwater wetlands in the Florida Everglades. We tracked photosynthesis, respiration, and growth at water levels of −10 (control), 10 (shallow), and 35 cm (deep) with reference to soil surface over 6 months.

Results

The response of photosynthesis to inundation was nonlinear. Specifically, photosynthetic capacity (Amax) declined by 25% in sawgrass and by 70% in muhly grass after 1–2 months of inundation. After 4 months, Amax of muhly grass in the deep‐water treatment declined to near zero. Inundated sawgrass maintained similar leaf respiration and growth rates as the control, whereas inundated muhly grass suppressed both respiration and growth. At the end of the experiment, sawgrass had similar nonstructural carbohydrate pools in all treatments. By contrast, muhly grass in the deep‐water treatment had largely depleted sugar reserves but maintained a similar starch pool as the control, which is critical for post‐stress recovery.

Conclusions

Overall, the two species exhibited nonlinear and contrasting patterns of carbon uptake and use under inundation stress, which ultimately defines their strategies of surviving regularly flooded habitats. The results suggest that a future scenario with more intensive inundation, due to the water management and climate change, may weaken the dominance of muhly grass in many freshwater wetlands of the Everglades.
Ecological and phylogenetic constraints determine the stage of anthetic ovule development in orchids
Authors: Mayer Juliana Lischka Sampaio , Scopece Giovanni , Barone Lumaga Maria Rosaria , Coiro Mario , Pinheiro Fabio , Cozzolino Salvatore
Published: October 2021

Premise

Unlike most flowering plants, orchid flowers have under‐developed ovules that complete development only after pollination. Classical studies reported variation in the stage in which ovule development is arrested, but the extent of this variation and its evolutionary and ecological significance are unclear.

Methods

Here, we used light microscopy to observe ovule development at anthesis for 39 species not previously studied and surveyed the literature gaining information on 94 orchid species. Tropical and temperate members of all five orchid subfamilies as well as species with contrasting pollination strategies (rewarding versus deceptive) and life forms (epiphytic versus terrestrial) were represented. We analyzed the data using statistical comparisons and a phylogenetic generalized least square (PGLS) analysis.

Results

Apostasioideae, the sister to the rest of the orchids, have mature ovules similar to other Asparagales, while under‐differentiated ovules are present in the other subfamilies. Ovule developmental stages showed high variation even among closely related groups. Ovules were more developed in terrestrial than in epiphytic, in temperate than in tropical, and in rewarding than in deceptive pollination orchid species. This latter comparison was also significant in the PGLS analysis.

Conclusions

These results suggest that ovule developmental stage in orchids can be shaped by ecological factors, such as seasonality and pollination strategy, and can be selected for optimizing female reproductive investment.
Chronic lymphocytic leukemia: 2022 update on diagnostic and therapeutic procedures
Authors: Hallek Michael , Al‐Sawaf Othman
Published: October 2021

Disease overview

Chronic lymphocytic leukemia (CLL) is one of the most frequent types of leukemia. It typically occurs in elderly patients and has a highly variable clinical course. Leukemic transformation is initiated by specific genomic alterations that interfere with the regulation of proliferation and of apoptosis in clonal B‐cells.

Diagnosis

The diagnosis is established by blood counts, blood smears, and immunophenotyping of circulating B‐lymphocytes, which identify a clonal B‐cell population carrying the CD5 antigen as well as typical B‐cell markers.

Prognosis and staging

The clinical staging systems provide prognostic information by using the results of physical examination and blood counts. Various biological and genetic markers provide additional prognostic information. Deletions of the short arm of chromosome 17 (del[17p]) and/or mutations of the TP53 gene predict resistance to chemoimmunotherapy and a shorter time to progression with most targeted therapies. The CLL international prognostic index integrates genetic, biological, and clinical variables to identify distinct risk groups of patients with CLL.

Therapy

Only patients with active or symptomatic disease or with advanced Binet or Rai stages require therapy. When treatment is indicated, several therapeutic options exist: a combination of the B‐cell lymphoma 2 (BCL2) inhibitor venetoclax with obinutuzumab, monotherapy with inhibitors of Bruton tyrosine kinase (BTK) such as ibrutinib and acalabrutinib, or chemoimmunotherapy. At relapse, the initial treatment may be repeated, if the treatment‐free interval exceeds 3 years. If the disease relapses earlier, therapy should be changed using an alternative regimen. Patients with a del(17p) or TP53 mutation are usually resistant to chemotherapy and should, therefore, be treated with targeted agents.

Future challenges

Combinations of targeted agents are now being investigated to create efficient, potentially curative therapies of CLL with fixed duration. One of the most relevant questions currently addressed in clinical trials is the comparison of monotherapies with BTK inhibitors with fixed duration combination therapies. Moreover, the optimal sequencing of targeted therapies remains to be determined. Alternative therapies are needed for patients with BTK and BCL2 inhibitor double‐refractory disease.
Exercise‐induced changes of vital signs in adults with sickle cell disease
Authors: Johnson Solomon , Gordeuk Victor R. , Machado Roberto , Gibbs J. Simon R. , Hildesheim Mariana , Little Jane A. , Kato Gregory J. , Gladwin Mark T. , Nouraie Mehdi
Published: October 2021

The six‐minute walk test (6MWT) has been used in patients with sickle cell disease (SCD), in conjunction with tricuspid regurgitant velocity (TRV) and plasma N‐terminal pro‐brain natriuretic peptide (NT‐pro BNP), to assess risk of having pulmonary hypertension. Exercise‐induced vital sign changes (VSCs) are predictors of clinical outcomes in other diseases. In this study, we assess the predictors and prognostic value of 6MWT VSC in adult SCD patients. Data from a multinational study of SCD patients (Treatment of Pulmonary Hypertension with Sildenafil: walk‐PHaSST) were used to calculate the 6MWT VSC. Predictors of VSC were identified by a multivariable analysis, and a survival analysis was conducted by the Cox proportional hazard method. An increase in heart rate was observed in 90% of the 630 SCD adults, 77% of patients had an increase in systolic blood pressure (SBP), and 50% of patients had a decrease in oxygen saturation. TRV (odds ratio [OR] = 1.82, p = .020), absolute reticulocyte count (OR = 1.03, p < .001), and hemoglobin (OR = 0.99, p = .035) predicted oxygen desaturation ≥ 3% during the 6MWT. In the adjusted analysis, SBP increase during the 6MWT was associated with improved survival (hazards ratio = 0.3, 95% confidence interval: 0.1–0.8). Increases in heart rate and blood pressure, as well as oxygen desaturation, are common in adults with SCD during the 6MWT. VSC is associated with markers of anemia and TRV and can be used for risk stratification. Any increase in SBP during the 6MWT was associated with improved survival and may be indicative of a patient's ability to increase stroke volume.
INTU‐related oral‐facial‐digital syndrome XVII: Clinical spectrum of a rare disorder
Authors: Yakar Omer , Tatar Abdulgani
Published: October 2021

Oral‐facial‐digital syndromes (OFDSs) as a subgroup of ciliopathies are rare genetic disorders characterized by the association of abnormalities of the face, oral cavity, and extremities. OFDS XVII is a recently described subtype of OFDS that presents with developmental delay, facial dysmorphism, high palate, tongue nodules, brain malformations, cardiac anomaly, polydactyly, renal malformation, and various other findings. OFDS XVII is caused by biallelic variants in INTU gene and is inherited autosomal recessively. Intu is part of the CPLANE protein module that has an essential role in the ciliary transport system and function. INTU pathogenic variants have been reported in two patients with OFDS XVII, in two patients with short‐rib thoracic dysplasia‐20 with polydactyly (SRTD20), and one with nephronophthisis so far. We report the third family in the literature with OFDS XVII, with urogenital malformations as an additional finding.
A patient with compound heterozygosity of SMPD4: Another example of utility of exome‐based copy number analysis in autosomal recessive disorders
Authors: Yamada Mamiko , Suzuki Hisato , Shima Taiki , Uehara Tomoko , Kosaki Kenjiro
Published: October 2021

For the efficient diagnosis of rare and undiagnosed diseases, the parallel detection of copy number variants (CNVs) and single nucleotide variants using exome analysis is required. Recently, our group reported the usefulness of a program called EXCAVATOR2, which screens for CNVs from aligned exome data in bam format. This method is expected to contribute to the identification of structural variants and to improve the diagnosis rate, especially for the diagnosis of autosomal recessive disease, when a conventional exome analysis identifies a pathogenic variant in one allele but not the other. Here we report a 2‐year‐old Japanese boy with an undiagnosed disease. He had severe neonatal asphyxia, severe intellectual disability, intractable seizures, cerebellar and brainstem hypoplasia and dysmorphic features including a prominent supraorbital ridge, thin upper lip, and prominent antihelix. An exome analysis reinforced with a copy number analysis using the EXCAVATOR2 method revealed that the patient had a hemizygous variant in chr2(GRCh37):g.130925108G>A, NM_017951.4 c.832C>T, p.(Arg278*) in SMPD4 that was derived from his father and a deletion of SMPD4 derived from his mother. The presence of the deletion spanning SMPD4 was confirmed by short‐read and long‐read whole‐genome sequencing. The successful diagnosis of this reported patient demonstrates the diagnostic utility of EXCAVATOR2 and overcomes the weakness of exome analysis for the detection of autosomal recessive diseases in nonconsanguineous families, significantly impacting genetic counseling for family planning.
Tau‐Atrophy Variability Reveals Phenotypic Heterogeneity in Alzheimer's Disease
Authors: Das Sandhitsu R. , Lyu Xueying , Duong Michael Tran , Xie Long , McCollum Lauren , de Flores Robin , DiCalogero Michael , Irwin David J. , Dickerson Bradford C. , Nasrallah Ilya M. , Yushkevich Paul A. , Wolk David A. ,   Alzheimer's Disease Neuroimaging Initiative
Published: October 2021

Objective

Tau neurofibrillary tangles (T) are the primary driver of downstream neurodegeneration (N) and subsequent cognitive impairment in Alzheimer's disease (AD). However, there is substantial variability in the T‐N relationship – manifested in higher or lower atrophy than expected for level of tau in a given brain region. The goal of this study was to determine if region‐based quantitation of this variability allows for identification of underlying modulatory factors, including polypathology.

Methods

Cortical thickness (N) and 18F‐Flortaucipir SUVR (T) were computed in 104 gray matter regions from a cohort of cognitively‐impaired, amyloid‐positive (A+) individuals. Region‐specific residuals from a robust linear fit between SUVR and cortical thickness were computed as a surrogate for T‐N mismatch. A summary T‐N mismatch metric defined using residuals were correlated with demographic and imaging‐based modulatory factors, and to partition the cohort into data‐driven subgroups.

Results

The summary T‐N mismatch metric correlated with underlying factors such as age and burden of white matter hyperintensity lesions. Data‐driven subgroups based on clustering of residuals appear to represent different biologically relevant phenotypes, with groups showing distinct spatial patterns of higher or lower atrophy than expected.

Interpretation

These data support the notion that a measure of deviation from a normative relationship between tau burden and neurodegeneration across brain regions in individuals on the AD continuum captures variability due to multiple underlying factors, and can reveal phenotypes, which if validated, may help identify possible contributors to neurodegeneration in addition to tau, which may ultimately be useful for cohort selection in clinical trials. ANN NEUROL 2021;90:751–762
Structure–Reactivity Relationship for Nano‐Catalysts in the Hydrogenation/Dehydrogenation Controlled Reaction Systems
Authors: Shen Tonghao , Yang Yuqi , Xu Xin
Published: October 2021

For the activity of a nano‐catalyst, a general and quantitative solution to building direct structure–reactivity relationship has not yet been established. On top of the first‐principle‐based kinetic Monte Carlo (KMC) simulations, we developed a model to build the adsorption site dependence of the activity. We applied this model to study the nano effects of Cu catalysts in the water‐gas shift reaction. By accumulating the activities of different adsorption sites, our model satisfactorily reproduced the experimental apparent activation energies for catalysts with sizes over hundreds of nanometers, which were out of reach for conventional KMC simulations. Our results disclose that, even for a cubic catalyst with size of 877 nm, its activity can still be closely related to the activity of edge sites, instead of only the exposed Cu(100) facets as might be expected. The present model is expected to be useful for systems that are controlled by the hydrogenation/dehydrogenation processes.
Non‐uniform Photoinduced Unfolding of Supramolecular Polymers Leading to Topological Block Nanofibers
Authors: Tashiro Keigo , Katayama Kosuke , Tamaki Kenta , Pesce Luca , Shimizu Nobutaka , Takagi Hideaki , Haruki Rie , Hollamby Martin J. , Pavan Giovanni M. , Yagai Shiki
Published: October 2021

Synthesis of one‐dimensional nanofibers with distinct topological (higher‐order structural) domains in the same main chain is one of the challenging topics in modern supramolecular polymer chemistry. Non‐uniform structural transformation of supramolecular polymer chains by external stimuli may enable preparation of such nanofibers. To demonstrate feasibility of this post‐polymerization strategy, we prepared a photoresponsive helically folded supramolecular polymers from a barbiturate monomer containing an azobenzene‐embedded rigid π‐conjugated scaffold. In contrast to previous helically folded supramolecular polymers composed of a more flexible azobenzene monomer, UV‐light induced unfolding of the newly prepared helically folded supramolecular polymers occurred nonuniformly, affording topological block copolymers consisting of folded and unfolded domains. The formation of such blocky copolymers indicates that the photoinduced unfolding of the helically folded structures initiates from relatively flexible parts such as termini or defects. Spontaneous refolding of the unfolded domains was observed after visible‐light irradiation followed by aging to restore fully folded structures.
One‐Pot Green Process to Synthesize MXene with Controllable Surface Terminations using Molten Salts
Authors: Shen Miao , Jiang Weiyan , Liang Kun , Zhao Sufang , Tang Rui , Zhang Linjuan , Wang Jian‐Qiang
Published: October 2021

Surface terminations of two‐dimensional MXene (Ti3C2Tx) considerably impact its physicochemical properties. Commonly used etching methods usually introduce ‐F surface terminations or metallic impurities in MXene. We present a new molten‐salt‐assisted electrochemical etching method to synthesize fluorine‐free Ti3C2Cl2. Using electrons as reaction agents, cathode reduction and anode etching can be spatially isolated; thus, no metallics are present in the Ti3C2Cl2 product. The surface terminations can be in situ modified from −Cl to −O and/or −S, which considerably shortens the modification steps and enriches the variety of surface terminations. The obtained −O‐terminated Ti3C2Tx are excellent electrode materials for supercapacitors, exhibiting capacitances of 225 F g−1 at 1.0 Ag−1, good rate performance (91.1 % at 10 Ag−1), and excellent capacitance retention (100 % after 10000 charge/discharge cycles at 10 Ag−1), which is superior to multi‐layered Ti3C2Tx prepared by other etching methods.
Luminescence Ratiometric Nanothermometry Regulated by Tailoring Annihilators of Triplet–Triplet Annihilation Upconversion Nanomicelles
Authors: Li Lin , Zhang Chun , Xu Lei , Ye Changqing , Chen Shuoran , Wang Xiaomei , Song Yanlin
Published: October 2021

Triplet–triplet annihilation (TTA) upconversion is a special non‐linear photophysical process that converts low‐energy photons into high‐energy photons based on sensitizer/annihilator pairs. Here, we constructed a novel luminescence ratiometric nanothermometer based on TTA upconversion nanomicelles by encapsulating sensitizer/annihilator molecules into a temperature‐sensitive amphiphilic triblock polymer and obtained good linear relationships between the luminescence ratio (integrated intensity ratio of upconverted luminescence peak to the downshifted phosphorescence peak) and the temperature. We also found chemical modification of annihilators would rule out the interference of the polymer concentration and stereochemical engineering of annihilators would readily regulate the thermal sensitivity.
Tetraphenylethylene‐Featured Fluorescent Supramolecular Nanoparticles for Intracellular Trafficking of Protein Delivery and Neuroprotection
Authors: Liu Ji , Sheng Jinhan , Shao Leihou , Zheng Qizhen , Li Wenting , Chen Xianghan , Mao Lanqun , Wang Ming
Published: October 2021

The delivery of protein into mammalian cells enables the dissection and manipulation of biological processes; however, this potency is challenged by the lack of an efficient protein delivery tool and a means to monitor its intracellular trafficking. Herein, we report that the hierarchical self‐assembly of tetraphenylethylene (TPE)‐featured metal–organic cages (MOCs) and β‐cyclodextrin‐conjugated polyethylenimine can generate fluorescent supramolecular nanoparticles (FSNPs) to deliver protein into neural cells, a cell line that is hard to transfect using conventional strategy. Further, the aggregation‐induced emission (AIE) of TPE enabled the fluorescent monitoring of cytosolic protein release. It is found that FSNPs can deliver and release protein into cytosol for subcellular targeting as fast as 18 h post‐delivery. Moreover, the delivery of molecular chaperone DJ‐1 using FSNPs activates MAPK/ERK signaling of neural cells to protect cells from oxidative stress.
Structural and Molecular Basis of the Catalytic Mechanism of Geranyl Pyrophosphate C6‐Methyltransferase: Creation of an Unprecedented Farnesyl Pyrophosphate C6‐Methyltransferase
Authors: Tsutsumi Hayama , Moriwaki Yoshitaka , Terada Tohru , Shimizu Kentaro , Shin‐ya Kazuo , Katsuyama Yohei , Ohnishi Yasuo
Published: October 2021

Prenyl pyrophosphate methyltransferases enhance the structural diversity of terpenoids. However, the molecular basis of their catalytic mechanisms is poorly understood. In this study, using multiple strategies, we characterized a geranyl pyrophosphate (GPP) C6‐methyltransferase, BezA. Biochemical analysis revealed that BezA requires Mg2+ and solely methylates GPP. The crystal structures of BezA and its complex with S‐adenosyl homocysteine were solved at 2.10 and 2.56 Å, respectively. Further analyses using site‐directed mutagenesis, molecular docking, molecular dynamics simulations, and quantum mechanics/molecular mechanics calculations revealed the molecular basis of the methylation reaction. Importantly, the function of E170 as a catalytic base to complete the methylation reaction was established. We also succeeded in switching the substrate specificity by introducing a W210A substitution, resulting in an unprecedented farnesyl pyrophosphate C6‐methyltransferase.
Identification of Inhibitors of Cholesterol Transport Proteins Through the Synthesis of a Diverse, Sterol‐Inspired Compound Collection
Authors: Whitmarsh‐Everiss Thomas , Olsen Asger Hegelund , Laraia Luca
Published: October 2021

Cholesterol transport proteins regulate a vast array of cellular processes including lipid metabolism, vesicular and non‐vesicular trafficking, organelle contact sites, and autophagy. Despite their undoubted importance, the identification of selective modulators of this class of proteins has been challenging due to the structural similarities in the cholesterol‐binding site. Herein we report a general strategy for the identification of selective inhibitors of cholesterol transport proteins via the synthesis of a diverse sterol‐inspired compound collection. Fusion of a primary sterol fragment to an array of secondary privileged scaffolds led to the identification of potent and selective inhibitors of the cholesterol transport protein Aster‐C, which displayed a surprising preference for the unnatural‐sterol AB‐ring stereochemistry and new inhibitors of Aster‐A. We propose that this strategy can and should be applied to any therapeutically relevant sterol‐binding protein.
Oil–Water–Oil Triphase Synthesis of Ionic Covalent Organic Framework Nanosheets
Authors: Guo Zheyuan , Jiang Haifei , Wu Hong , Zhang Leilang , Song Shuqing , Chen Yu , Zheng Chenyang , Ren Yanxiong , Zhao Rui , Li Yonghong , Yin Yan , Guiver Michael D. , Jiang Zhongyi
Published: October 2021

Ionic covalent organic framework nanosheets (iCOFNs) with long‐range ordered and mono‐dispersed ionic groups hold great potential in many advanced applications. Considering the inherent drawbacks of oil–water biphase method, herein, we explore an oil–water–oil triphase method based on phase engineering strategy for the bottom‐up synthesis of iCOFNs. The middle water phase serves as a confined reaction region, and the two oil phases are reservoirs for storing and supplying monomers to the water phase. A large aqueous space and low monomer concentration lead to the anisotropic gradual growth of iCOFNs into few‐layer thickness, large lateral size, and high crystallinity. Notably, the resulting three cationic and anionic iCOFNs exhibit ultra‐high aspect ratios of up to 20,000. We further demonstrate their application potential by processing into ultrathin defect‐free COF membranes for efficient biogas separation. Our triphase method may offer an alternative platform technology for the synthesis and innovative applications of iCOFNs.
Achieving Short‐Wavelength Phase‐Matching Second Harmonic Generation in Boron‐Rich Borosulfate with Planar [BO3] Units
Authors: Li Zijian , Jin Wenqi , Zhang Fangfang , Chen Zilong , Yang Zhihua , Pan Shilie
Published: October 2021

Ultraviolet (UV) nonlinear optical (NLO) crystals which can produce short‐wavelength lasers via a direct second harmonic generation (SHG) process are of great importance in modern laser technology. Currently, the exploration of UV NLO crystals in borosulfates is nearly stagnant since the non‐phase matching (PM) property lies on the small birefringence induced by the intrinsically small optical anisotropy of the tetrahedral groups. Herein, for the first time, the planar [BO3] units were introduced into borosulfates leading to a boron‐rich borosulfate (NH4)2B4SO10 with unprecedented [B4SO10]∞ layers and evidently enhanced birefringence. To the best of our knowledge, it achieves the shortest SHG PM wavelength of 252 nm in all reported borosulfates with deep UV cutoff edge (184 nm), large SHG response (1.1×KDP at 1064 nm and 0.15×β‐BBO at 532 nm) and large birefringence (0.053 at 1064 nm) and is easy to grow single crystals via simple chemical vapor deposition method. These results confirm the feasibility of utilizing planar [BO3] units to optimize birefringence of borosulfates, and also open up broad prospects for UV NLO crystals in boron‐rich borosulfates.
Engineering Lattice Oxygen Activation of Iridium Clusters Stabilized on Amorphous Bimetal Borides Array for Oxygen Evolution Reaction
Authors: Wang Chen , Zhai Panlong , Xia Mingyue , Wu Yunzhen , Zhang Bo , Li Zhuwei , Ran Lei , Gao Junfeng , Zhang Xiaomeng , Fan Zhaozhong , Sun Licheng , Hou Jungang
Published: October 2021

Developing robust oxygen evolution reaction (OER) catalysts requires significant advances in material design and in‐depth understanding for water electrolysis. Herein, we report iridium clusters stabilized surface reconstructed oxyhydroxides on amorphous metal borides array, achieving an ultralow overpotential of 178 mV at 10 mA cm−2 for OER in alkaline medium. The coupling of iridium clusters induced the formation of high valence cobalt species and Ir–O–Co bridge between iridium and oxyhydroxides at the atomic scale, engineering lattice oxygen activation and non‐concerted proton‐electron transfer to trigger multiple active sites for intrinsic pH‐dependent OER activity. The lattice oxygen oxidation mechanism (LOM) was confirmed by in situ 18O isotope labeling mass spectrometry and chemical recognition of negative peroxo‐like species. Theoretical simulations reveal that the OER performance on this catalyst is intrinsically dominated by LOM pathway, facilitating the reaction kinetics. This work not only paves an avenue for the rational design of electrocatalysts, but also serves the fundamental insights into the lattice oxygen participation for promising OER application.
Simultaneous Kinetic Resolution and Asymmetric Induction within a Borrowing Hydrogen Cascade Mediated by a Single Catalyst
Authors: Jin Ming Yu , Zhou Yali , Xiao Dengmengfei , You Yipeng , Zhen Qianqian , Tao Guanyu , Yu Peiyuan , Xing Xiangyou
Published: October 2021

The mechanistic uniqueness and versatility of borrowing hydrogen catalysis provides an opportunity to investigate the controllability of a cascade reaction, and more importantly, to realize either one or both of chiral recognition and chiral induction simultaneously. Here we report that, in a borrowing hydrogen cascade starting from racemic allylic alcohols, one of the enantiomers could be kinetically resolved, while the other enantiomer could be purposely converted to various targeted products, including α,β‐unsaturated ketones, β‐functionalized ketones and γ‐functionalized alcohols. By employing a robust Ru‐catalyst, both kinetic resolution and asymmetric induction were achieved with remarkable levels of efficiency and enantioselectivity. Density functional theory (DFT) calculations suggest that corresponding catalyst–substrate π–π interactions are pivotal to realize the observed stereochemical diversity.
Real‐Time Simultaneous Imaging of Acidification and Proteolysis in Single Phagosomes Using Bifunctional Janus‐Particle Probes
Authors: Lee Seonik , Zhang Zihan , Yu Yan
Published: October 2021

The digestion of pathogens inside phagosomes by immune cells occurs through a sequence of reactions including acidification and proteolysis, but how the reactions are orchestrated in the right order is unclear due to a lack of methods to simultaneously measure more than one reaction in phagosomes. Here we report a bifunctional Janus‐particle probe to simultaneously monitor acidification and proteolysis in single phagosomes in live cells. Each probe consists of a pH reporter and a proteolysis reporter that are spatially separated but function concurrently. Using the Janus probes, we found the acidic pH needed to initiate and maintain proteolysis, revealing the mechanism for the sequential occurrence of both reactions during pathogen digestion. We showed how bacterium‐derived lipopolysaccharides alter the acidification and proteolysis in phagosomes. This study showcases Janus‐particle probes as a generally applicable tool for monitoring multiple reactions in intracellular vesicles.
Sequential Selective C−H and C(sp3)−+P Bond Functionalizations: An Entry to Bioactive Arylated Scaffolds
Authors: Babu K. Naresh , Massarwe Fedaa , Shioukhi Israa , Masarwa Ahmad
Published: October 2021

Organophosphonium salts containing C(sp3)−+P bonds are among the most utilized reagents in organic synthesis for constructing C−C double bonds. However, their use as C‐selective electrophilic groups is rare. Here, we explore an efficient and general transition‐metal‐free method for sequential chemo‐ and regioselective C−H and C(sp3)−+P bond functionalizations. In the present study, C−H alkylation resulting in the synthesis of benzhydryl triarylphosphonium salts was achieved by one‐pot, four‐component cross‐coupling reactions of simple and commercially available starting materials. The utility of the resulting phosphonium salt building blocks was demonstrated by the chemoselective post‐functionalization of benzylic C(sp3)−+PPh3 groups to achieve aminations, thiolations, and arylations. In this way, benzhydrylamines, benzhydrylthioethers, and triarylmethanes, structural motifs that are present in many pharmaceuticals and agrochemicals, are readily accessed. These include the synthesis of two anticancer agents from simple materials in only two to three steps. Additionally, a protocol for late‐stage functionalization of bioactive drugs has been developed using benzhydrylphosphonium salts. This new approach should provide novel transformations for application in both academic and pharmaceutical research.
Donor/π‐Bridge Manipulation for Constructing a Stable NIR‐II Aggregation‐Induced Emission Luminogen with Balanced Phototheranostic Performance**
Authors: Yan Dingyuan , Xie Wei , Zhang Jianyu , Wang Lei , Wang Dong , Tang Ben Zhong
Published: October 2021

Owing to their versatile functionality and tunable energy dissipation, aggregation‐induced emission luminogens (AIEgens) have emerged as a potential platform for multimodal theranostics. Nevertheless, the construction of AIE‐active phototheranostic agents in the second near‐infrared window (NIR‐II, 1000–1700 nm), which allows superior resolution and minimized photodamage, is still a formidable challenge. Herein, benzo[c]thiophene serves as an electron‐rich and bulky donor (D)/π‐bridge, which can enlarge the conjugation length and distort the backbone of an AIEgen. By precise D/π‐bridge engineering, highly stable NIR‐II AIEgen DPBTA‐DPTQ nanoparticles are obtained with acceptable NIR‐II fluorescence quantum yield and excellent photothermal conversion efficiency. In addition, the spatial conformation of DPBTA‐DPTQ is determined for the first time by X‐ray single crystal diffraction and theoretical simulations. DPBTA‐DPTQ NPs have good biocompatibility and show efficient photothermal therapeutic effects in in vitro tests. Furthermore, DPBTA‐DPTQ NPs were used in fluorescence‐photoacoustic‐photothermal trimodal imaging‐guided photothermal eradication of tumors in HepG2 and B16‐F10 tumor‐xenografted mice.
DNA Tiling Enables Precise Acylation‐Based Labeling and Control of mRNA
Authors: Xiao Lu , Jun Yong Woong , Kool Eric T.
Published: October 2021

Methods for the site‐selective labeling of long, native RNAs are needed for studying mRNA biology and future therapies. Current approaches involve engineering RNA sequences, which may alter folding, or are limited to specific sequences or bases. Here, we describe a versatile strategy for mRNA conjugation via a novel DNA‐tiling approach. The method, TRAIL, exploits a pool of “protector” oligodeoxynucleotides to hybridize and block the mRNA, combined with an “inducer” DNA that extrudes a reactive RNA loop for acylation at a predetermined site. Using TRAIL, an azido‐acylimidazole reagent was employed for labeling and controlling RNA for multiple applications in vitro and in cells, including analysis of RNA‐binding proteins, imaging mRNA in cells, and analysis and control of translation. The TRAIL approach offers an efficient and accessible way to label and manipulate RNAs of virtually any length or origin without altering native sequence.
Synthesis of Cu(II) complexes by N,O‐donor ligand transformation and their catalytic role in visible‐light‐driven alcohol oxidation
Authors: Ranjan Rishi , Kundu Bidyut Kumar , Kyarikwal Reena , Ganguly Rakesh , Mukhopadhyay Suman
Published: October 2021

Visible‐light‐driven photoreactions using metal complexes as catalysts are currently a research hotspot in terms of the development of environmentally friendly sustainable processes. To develop potential copper‐based photocatalysts, a Mannich base ligand, namely, 2,4‐dichloro‐6‐((4‐(2‐hydroxyethyl)piperazin‐1‐yl)methyl)phenol (H2L), has been synthesized and characterized. Two copper complexes [Cu (HL1)] (1) and [Cu (HL2)] (2) have been obtained from H2L, where the ligand undergoes an unprecedented transformation plausibly via oxidation of piperazine ring to ketone, subsequent oxidation of enol and nucleophilic attack of methanol followed by hydrolysis of amide bond, resulting piperazine ring cleavage. Under the irradiation of visible light, these catalysts can oxidize primary alcohols into corresponding aldehydes with very good conversion and high selectivity in the presence of molecular oxygen. The photocatalysts could be recovered almost quantitatively after completion of the catalytic cycle and recycled at least four times without much depreciation of catalytic activity. A plausible mechanistic pathway for alcohol oxidation has been explored through electrospray ionization mass spectrometry (ESI‐MS) spectrometric, cyclic voltammetry, UV–vis, and computational study.
Stimuli‐responsive polymeric additives for anticorrosion
Authors: Auepattana‐Aumrung Krisada , Phakkeeree Treethip , Crespy Daniel
Published: October 2021

Corrosion is a significant issue for metals and alloys items because it critically affects their lifetimes. To protect the metal from corrosion, corrosion inhibitors can be added into coatings, but the inhibitor can leach into the environment. Polymer‐corrosion inhibitor conjugates are developed to solve this problem. However, corrosion can occur in various fields of applications, which then need a different level and type of metal's protection. β‐thiopropionate and ester linkages between polymer and inhibitor are selected as model for very labile and moderately labile linkages, respectively. The rate of inhibitor's release is controlled by the linkage of conjugated payloads. Corrosion measurements indicated that polymers with the β‐thiopropionate linkage are suitable for severe corrosion and short‐term applications, whereas the polymers with ester linkage can be used for mild corrosion and long‐term applications.
Sustainable textile fibers of bioderived polylactide/poly(pentamethylene 2,5‐furanoate) blends
Authors: Perin Davide , Fredi Giulia , Rigotti Daniele , Soccio Michelina , Lotti Nadia , Dorigato Andrea
Published: October 2021

Furanoate polyesters are emerging as promising bioderived polymers that could replace petrochemical‐derived polyesters in several applications, for example, the textile field. Here, sustainable and fully bioderived fibers are wet‐spun by blending poly(lactic acid) (PLA) and poly(pentamethylene 2,5‐furanoate) (PPeF), with up to 50 wt% of PPeF. PLA/PPeF blends result as immiscible, with PPeF domains homogeneously distributed within the PLA matrix, as shown by scanning electron micrographs. The immiscibility is confirmed by differential scanning calorimetry, as the glass transition temperature of PLA is unaffected by PPeF. The immiscibility and poor adhesion between PLA and PPeF are responsible for the decrease in stress at break and elongation at break from 30.1 MPa and 127%, of PLA fibers, to 3.5 MPa and 1.9%, at high PPeF amounts. However, the addition of PPeF strongly decreases the PLA's tendency to absorb water and retain the processing solvents, showing a mass loss decrease from 3.1% for PLA fibers to 1% for fibers containing 50 wt% PPeF, thereby addressing one of the main drawbacks of PLA. These results, although preliminary, offer new directions for future works on innovative and sustainable fibers based on furanoate polyesters.
Functionalization of PMMA/TiO2 nanocomposites: Synthesis, characterization and their antioxidant and antibacterial evaluation
Authors: Singh Paramjit , Mirza Azar Ullah , Mondal Aftab Hossain , Mukhopadhyay Kasturi , Nishat Nahid
Published: October 2021

The present work reports the functionalization of PMMA and its nanocomposites were synthesized via simple solution mixing method. Functionalization of PMMA with different amino containing groups, that is, ethylene diamine (ED) and 4‐amino benzoic acid (PA) and used with low dosage (1 wt% and 3 wt%) of TiO2 nanoparticles (NPs) to form nanocomposites. The morphology was determined by SEM, average particle size (50 nm) of TiO2 NPs was measured by TEM. The pore radius (14.47 A°) and specific surface area (157.89 m2/g) of TiO2 NPs were measured by BET analysis. FT‐IR and NMR analysis confirms the functionalization of PMMA. The antioxidant activity of functionalized PMMA and its nanocomposites have been analyzed by using 2,2 diphenyl‐1‐picryhydrazyl (DPPH) assay. The antibacterial activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) of functionalized polymer nanocomposites were investigated. The result revealed that functionalized PMMA (PMPA) shows maximum antioxidant activity. The increase in concentration of TiO2 NPs efficiently augments the bacterial inhibition against Gram‐negative and Gram‐positive bacteria. The maximum zone of inhibition (ZOI) was recorded against E. coli ATCC 25922 (30 mm) and S. aureus ATCC 29213 (31 mm) and minimum inhibitory concentration (MIC) over E. coli (64 μg/ml) and S. aureus (32 μg/ml) by PMPA2. The synthesized functionalized PMMA nanocomposites can be considered as promising material for biological applications.
Crystal growth of PPS nanofibers during annealing studied by solid‐state 13C CPMAS NMR
Authors: Asano Atsushi , Koyama Hiroyuki , Suzuki Akihiro
Published: October 2021

Initial crystalline phase growth property for poly(p‐phenylene sulfide) (PPS) nanofibers during annealing are studied by means of the 13C high‐resolution solid‐state cross‐polarization/magic‐angle‐spinning NMR (13C CPMAS NMR) with spectral editing procedure using the difference in 1H spin‐lattice relaxation time in the rotating frame (T1ρH) between the crystalline and non‐crystalline phases. The PPS nanofibers are prepared by drawing the solid microfibers melted by a high‐power carbon dioxide (CO2) laser with supersonic jet velocity of 300–600 ms−1 in a vacuum chamber (CLSD method). The crystallinity and molecular orientation of the pristine drawn PPS nanofibers increase with decrease of the chamber pressure (pch). The growing process and the ordered chain packing of the crystalline phase during annealing depend on the initial chain orientation. The low pressures at pch = 30 and 10 kPa significantly relate to the initial nucleation growth of the PPS nanofibers. In the initial crystal growth of PPS nanofibers obtained at pch = 30 kPa for the low temperature annealing, the rearrangement of chains occurs, but for those at pch = 10 kPa the rearrangement does not occur. This is because the highly ordered chain alignments and packing are already achieved for PPS nanofibers obtained at pch = 10 kPa.
Nationalism and economic openness: The cross‐country evidence
Authors: Breunig Robert , Agarwal Vishesh , Arfin Sadia , Weldeegzie Samuel , Zhang Tong
Published: October 2021

Using cross‐country data, we find little evidence that economic openness has an impact on the level of nationalism in countries. We use three waves of the World Values Survey from 1999 through 2014 combined with data on economic openness from the Penn World Tables. Across all three waves, we find no statistically significant relationship between economic openness and nationalism. However, there is evidence for a negative association between economic openness and nationalism from 2001 to 2007 and a positive association between 2007 and 2014. This corresponds to the rising nationalistic and anti‐trade sentiment evident throughout the world despite the general trend of increasing economic openness.
Do consumers care about morality? A review and framework for understanding morality's marketplace influence
Authors: Philipp‐Muller Aviva , Teeny Jacob D. , Petty Richard E.
Published: October 2021

There are many ways consumers' morality has been shown to impact their marketplace behavior. We present a theoretical framework for how to conceive of and study marketplace morality in an attempt to unify these disparate findings. First, we describe two common conceptualizations of marketplace morality: (a) the attribute‐level approach (where a product attribute fits within a category that is normatively considered moral) and (b) the person‐level approach (where consumers differ in the extent to which they dispositionally value morality). We then introduce a third conceptualization: (c) the attitude‐level approach (where consumers differ in the extent to which they see their relevant attitude as based in their morality). Through this approach, we demonstrate morality's predictive utility for consumers' marketplace behaviors and help explain why other research could have found mixed evidence for its influence. Moreover, we use this approach to illuminate four contexts in which consumers' morality is more likely to influence marketplace attitudes and thereby impact their behavior: when the consumer's attitude is emotional, value‐relevant, identity‐relevant, and/or conceived in a negative valence. We conclude with a discussion of some of the unique challenges to attitude moralization in the marketplace as well as implications for managers promoting morally positioned purchases.
Applicability of semi‐pro unmanned aircraft system for rapid archaeological documentation in forested areas
Authors: Kamnik Rok , Jelenko Saša Djura , Perc Matjaž Nekrep
Published: October 2021

This paper tests the applicability of an unmanned aerial system (UAS) in obtaining spatial data from archaeological sites in forested areas. Our case study discusses the remains of the anti‐Turkish fortifications called ‘Turške Šance’—the defensive ditches that are preserved in the area of the Preški vrh (Ravne na Koroškem, Slovenia). Up to 10 fortifications of various shapes and sizes were built in the last quarter of the 15th century. Today, they represent a unique archaeological site. A detailed geodetic survey of the site was performed and compared with results of photogrammetry using the DJI Phantom 4 PRO UAS drone and DJI Phantom camera. Furthermore, official Slovenian LiDAR data of the area were obtained, and archaeologic field surveys, in situ inspections and metal detector scanning were made. The points obtained from the total station were used for 3D modelling and taken as a reference. Drone photogrammetry was performed once per week to compare each point cloud with another using CloudCompare and to the reference one depending on the volume of the tree leaves which was estimated with green leaf index (GLI) and leaf area index (LAI). The increase of the tree leaves volume deteriorates the point cloud obtained with a UAS. The paper analyses how significant this influence is. As expected, the impact grows more severe with the increase in leaf mass from week to week.
A Cell‐Culture Technique to Encode Glyco‐Nanoparticles Selectivity
Authors: Subramani Balamurugan , Chaudhary Preeti Madhukar , Kikkeri Raghavendra
Published: October 2021

Nanoparticles (NPs) embedded with bioactive ligands such as carbohydrates, peptides, and nucleic acid have emerged as a potential tool to target biological processes. Traditional in vitro assays performed under statistic conditions may result in non‐specific outcome sometimes, mainly because of the sedimentation and self‐assembly nature of NPs. Inverted cell‐culture assay allows for flexible and accurate detection of the receptor‐mediated uptake and cytotoxicity of NPs. By combining this technique with glyco‐gold nanoparticles, cellular internalization and cytotoxicity were investigated. Regioselective glycosylation patterns and shapes of the NPs could tune the receptors′ binding affinity, resulting in precise cellular uptake of gold nanoparticles (AuNPs). Two cell lines HepG2 and HeLa were probed with galactosamine‐embedded fluorescent AuNPs, revealing significant differences in cytotoxicity and uptake mechanism in upright and invert in vitro cell‐culture assay, high‐specificity toward uptake, and allowing for a rapid screening and optimization technique.
Recent Advances in Polyallenes: Preparation, Self‐Assembly, and Stimuli‐Responsiveness
Authors: Wang Chao , Zou Hui , Liu Na , Wu Zong‐Quan
Published: October 2021

Polyallenes, as a typical type of reactive polymers, are of great significance and have aroused widespread interest because they contain double bonds that can be post‐modified into other functionalities to afford varieties of functional materials. This Minireview firstly highlights the recent advances in the preparation of polyallenes, including preparation of helical polyallenes through directly polymerization of chiral allene monomers or helix‐sense‐selective polymerization (HSSP) of achiral allene monomers, synthesis of 1,2‐regulated polyallenes and 2,3‐regulated polyallenes via selective polymerization of allene monomers, polymerization of allene monomers catalyzed by Ni(II)‐terminated poly(3‐hexylthiophene) (P3HT), and so on. Then, latest progress on the self‐assembly and stimuli‐responses of polyallene‐based diblock, ABA and ABC triblock copolymers is summarized. We hope this Minireview will inspire more interest in developing polyallenes and encourage further advances in functional materials.
Lipase‐mediated multicomponent synthesis of 1H‐Pyrazolo[1,2‐b]phthalazine‐5,10‐dione derivatives in a binary solvent medium
Authors: Dalal Kiran S. , Tayade Yogesh A. , Wagh Yogesh B. , Dalal Dipak S. , Chaudhari Bhushan L.
Published: October 2021

A new method for the synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐dione derivatives via lipase from the Aspergillus niger–catalyzed multicomponent reaction of aldehydes, malononitrile, and phthalhydrazide is reported herein for the first time. This novel method holds several advantages, including its efficiency, environmental friendliness, simple workup procedure, and good yield (70–86%). The effects of temperature, organic solvents, and water content were investigated. This protocol has the potential to replace traditional chemical synthesis routes for the synthesis of nitrogen‐containing heterocyclic compounds.