bluuebunny/crossref_metadata_2025 huggingface dataset:
Discovery and Characterization of a Baeyer‐Villiger Monooxygenase Using Sequence Similarity Network Analysis
Authors: Sakoleva Thaleia , Austin Harry P. , Tzima Chrysoula , Dörr Mark , Bornscheuer Uwe T.
Published: March 2023

Baeyer‐Villiger monooxygenases (BVMOs) are important flavin‐dependent enzymes which perform oxygen insertion reactions leading to valuable products. As reported in many studies, BVMOs are usually unstable during application, preventing a wider usage in biocatalysis. Here, we discovered a novel NADPH‐dependent BVMO which originates from Halopolyspora algeriensis using sequence similarity networks (SSNs). The enzyme is stable at temperatures between 10 °C to 30 °C up to five days after the purification, and yields the normal ester product. In this study, the substrate scope was investigated for a broad range of aliphatic ketones and the enzyme was biochemically characterized to identify optimum reaction conditions. The best substrate (86 % conversion) was 2‐dodecanone using purified enzyme. This novel BVMO could potentially be applied as part of an enzymatic cascade or in bioprocesses which utilize aliphatic alkanes as feedstock.
Infection and myelodysplasia: A case report of GATA2 deficiency in a South African patient
Authors: Nell Erica‐Mari , Cornellissen Helena , Hodkinson Katherine , Urban Michael F. , Bassa Fatima Cassim , Fazel Fatima Bibi , Wiggill Tracey , Irusen Semira , Chapanduka Zivanai C.
Published: March 2023

Rare diseases often result in delays in diagnosis. It is important to recognize conditions that have features of both inborn errors of immunity and predispose to myeloid neoplasia. Here we report a patient with GATA2 deficiency that presented with disseminated non‐tuberculous mycobacterial infection and pancytopenia secondary to myelodysplastic syndrome.
Pseudomyxoma peritonei induced by a well‐differentiated appendicular mucinous adenocarcinoma: An uncommon cause of isolated ascites in a young man patient
Authors: Randriamifidy Nitah Harivony , Ranaivoson Mirana Andoniaina Christiana , Ramiandrasoa Andriamampihantona Lalaoarifetra , Razafindrazoto Chantelli Iamblaudiot , Ranaivomanana Volahasina Francine , Hasina Laingonirina Domoina Harivonjy , Rakotomaharo Mialitiana , Rakotoniaina Henintsoa , Randrianiaina Antsa Fihobiana , Rasolonjatovo Anjaramalala Sitraka , Rakotozafindrabe Andry Lalaina Rinà , Rabenjanahary Tovo Harimanana , Razafimahefa Soloniaina Hélio , Rafaramino Florine , Ramanampamonjy Rado Manitrala
Published: March 2023

Pseudomyxoma peritonei (PMP) remains difficult to diagnose and has a reserved prognosis. Pseudomyxoma peritonei is a rare entity, of appendicular origin in the majority of cases. Its clinical symptomatology is not specific, and the diagnosis is evoked by imaging and surgery and confirmed by histology.
Insight into Electrochemical Promotion of Cu/Co3O4 Catalysts for the Reverse Water Gas Shift Reaction
Authors: Wang Ju , Couillard Martin , Baranova Elena A.
Published: March 2023

In this study, Copper‐modified Co3O4 (Cu/Co3O4) catalysts were investigated for the reverse water gas shift (RWGS) reaction at 200–400 °C under different CO2 : H2 ratios. It was found that the electrocatalytic performance of Co3O4 was improved by loading 4 weight percent (wt.%) Cu nanoparticles (average size: 13 nm), which could be then used as an electrode in electrochemical promotion of catalysis (EPOC) studies. Under the applied voltages of +2 V and −1 V, the catalytic rates were suppressed and increased by about 40 % and 14 %, respectively. This was due to the changes in the active oxidation states of Cu and Co caused by O2− migration under polarization, as confirmed by XPS, XRD, and cyclic voltammetry (CV). The study also revealed that the exchange current density (i0) was counter‐correlated with the open‐circuit catalytic rate (r0) and could serve as an informative tool for predicting the catalytic rate, which was demonstrated for the first time in the instance of RWGS reaction.
Mixing Efficiency of Viscous Fluid in a Multiple‐Impeller Agitated Tank
Authors: Shiue Angus , Chen Qianqiao , Chen Yi-Ting , Jeng Jyh-Cheng , Leggett Graham
Published: March 2023

The development of a multi‐impeller reactor for the mixing of non‐Newtonian fluids under full flow regime conditions depends on mixing time, power consumption, and mixing energy. These parameters must be well‐defined with 3‐blade propellers, 4‐pitched turbines, and 6‐flat‐blade turbines. An innovative expression of mixing time for the thermal pulse disturbance method is introduced. The Buckingham's π‐theorem was utilized to denominate and transfer dimensionless power and homogenization number. To achieve consistent mixing, the results indicated that axial flow of the 4‐pitched‐blade turbine is the most effective approach. The examined correlation is a functional tool to determine the mixing energy based on the measured specific power consumption and mixing time.
Oxanorbornene‐Fused Phenazine‐Pyrene Scaffolds with Different Configurations
Authors: Ye Liping , Miao Qian
Published: March 2023

New molecular scaffolds of C‐, Z‐ and box‐shaped configurations are constructed by fusing phenazine and pyrene units with oxanorbornene. As revealed by X‐ray crystallography, the C‐shaped molecules exhibit two interesting π‐π stacking modes of phenazine depending on the substituting groups, and the box‐shaped molecule accommodates two chloroform molecules in the cavity and forms H‐bonds with another four molecules of chloroform. The C‐ and Z‐shaped molecules as a pair of diastereomers exhibit almost the same charge transfer absorption and emission including positive solvatochromism, indicating that the intramolecular charge transfer between pyrene (π‐donor) and phenazine (π‐acceptor) is not dependent on the overall molecular geometry.
Electronic Structure and Aromaticity of an Unusual Cyclo[18]carbon Precursor, C18Br6**
Authors: Wang Xia , Liu Zeyu , Wang Jiaojiao , Lu Tian , Xiong Weiwei , Yan Xiufen , Zhao Mengdi , Orozco‐Ic Mesías
Published: March 2023

Herein, the electronic structure and bonding character of the stable cyclo[18]carbon (C18) precursor, C18Br6, are thoroughly characterized by molecular orbital (MO), density of states (DOS), bond order (BO), and interaction region indicator (IRI) analyses. The delocalization characters of out‐of‐plane and in‐plane π‐electrons (labeled as πout‐ and πin‐electrons, respectively) in bonding regions were examined using localized orbital locator (LOL) and electron localization function (ELF). The aromaticity was investigated, studying the molecular magnetic response to external magnetic field by computing the magnetically induced current density (Jind), iso‐chemical shielding surface (ICSS), anisotropy of the induced current density (AICD), and the induced magnetic field (Bind). All these analyses indicate that C18Br6 is a globally aromatic species with lower aromaticity than C18, and the blocking of in‐plane π‐conjugation (labeled as πin‐conjugation) by the presence of ‐Br substituents in it is the underlying cause for the weakening of molecular aromaticity.
Photocatalytic Aerobic Cyclization of N‐Propargylamides Enabled by Selenium‐π‐Acid Catalysis
Authors: Wang Yong‐Hao , Jiang You‐Qin , Zhang Yun‐Qian , Ling Yong , Ming Liang , Liu Gong‐Qing
Published: March 2023

A dual catalytic approach combining photocatalyst and selenium‐π‐acid synergy has been used to cyclized of N‐propargylamides. This method offers readily access to oxazole aldehydes under chemical oxidant‐free conditions with low catalyst loadings, where air acts as a terminal and gratuitous oxidant. The reaction is demonstrated with a range of substrates, including aryl and alkyl propargyl amides, and in the late‐stage functionalization of several amide‐containing drug molecules. Mechanistic studies suggest that the acridinium catalyst is able to oxidize diselenide and generate singlet oxygen (1O2), which is responsible for this transformation.
(Co‐)Oligomerization of Olefins to Hydrocarbon Fuels: Influence of Feed Composition and Pressure
Authors: Fuchs Constantin , Arnold Ulrich , Sauer Jörg
Published: March 2023

The co‐oligomerization of methanol‐based C2‐4 olefins on a heterogeneous nickel silica‐alumina catalyst enables the production of fuel‐range hydrocarbons. The objective of this study was the production of gasoline and jet fuel, which was achieved with an overall selectivity of above 90 %. The influence of olefin feed composition and pressure was investigated at 120 °C. By employing olefin mixtures instead of one single olefin, selectivity to specific chain lengths decreases and quantities of the individual products converge. An increase of olefin pressure from 16 to 32 bar slightly shifts the liquid products to shorter oligomers and raises feed conversion.
Fine Tuning of Donor‐Acceptor Structures in Fused‐Carbazole Containing Thermally Activated Delayed Fluorescence Materials towards High‐Efficiency OLEDs
Authors: Yuan Wenbo , Hu Weiyang , Wang Jian , Zhu Mengyuan , Shi Changsheng , Sun Ning , Tao Youtian
Published: March 2023

Comprehensive Summary

Conjugated fused‐ring structures have attracted extensive attention due to their high molecular rigidity to restrain excited‐state relaxation and non‐radiative decay, and further to enhance the luminance efficiency for emissive materials. Herein, we develop a series of donor‐acceptor type thermally activated delayed fluorescence (TADF) emitters by introducing fused‐ring 5H‐benzofuro[3,2‐c]carbazole (32BFCz) as electron donating unit. Through optimizing the numbers and structure of donor and acceptor moieties, three compounds named 32BFCzA, mCF3BFCzOXD and dCF3BFCzOXD are designed, which are composed by mono‐32BFCz/trifluoromethylpicolinonitrile, penta‐BFCz/3‐(trifluoromethyl)phenyl)‐1,3,4‐oxadiazol‐2‐yl)benzene and penta‐32BFCz/3,5‐bis(trifluoromethyl)phenyl)‐1,3,4‐oxadiazol‐2‐yl)benzene as donor/acceptor groups, respectively. They all exhibited green emission with peak value ranging from 532 to 540 nm. Through rationally tuning the donor/acceptor properties to reduce the distance between positive and negative charges, the ground state dipole moments decline from 8.93, 6.18 to 5.30 Debye, which further induced sequentially reduced singlet‐triplet energy splits (ΔESTs), increased photoluminescence quantum yields (PLQYs), enhanced reverse intersystem crossing rate (kRISCs) and diminished delayed fluorescence lifetime from 32BFCzA, mCF3BFCzOXD to dCF3BFCzOXD. Therefore, gradually increased external quantum efficiency (EQE) is accordingly achieved when employing them as emitters for TADF OLEDs. dCF3BFCzOXD with the mostly optimized donor/acceptor structures demonstrates the highest efficiency with maximum EQE to 21.4%. Our work provides guidelines on the design of high‐efficiency D‐A type TADF materials.
Clinical characteristics, treatment, and survival of 30 patients with gastrointestinal natural killer/T‐cell lymphoma
Authors: Liu Jia‐Xin , Liu Xin , Yang Yong , Liu Wei‐Ping , Wang Ying , He Xia , Zhang Li‐Ling , Qu Bao‐Lin , Qian Li‐Ting , Hou Xiao‐Rong , Qiao Xue‐Ying , Wang Hua , Li Gao‐Feng , Zhu Yuan , Cao Jian‐Zhong , Wu Jun‐Xin , Wu Tao , Zhu Su‐Yu , Shi Mei , Zhang Hui‐Lai , Su Hang , Zhang Yu‐Jing , Zhu Jun , Qi Shu‐Nan , Li Ye‐Xiong , Song Yu‐Qin
Published: March 2023

Background

The gastrointestinal (GI) tract is the second most frequent extranasal involvement site for ENKTL. This study aimed to explore the clinicopathological features, treatment models, survival outcomes, and prognosis of gastrointestinal ENKTL (GI‐ENKTL).

Methods

The clinical data of GI‐ENKTL patients were extracted from the China Lymphoma Collaborative Group (CLCG) database and were analyzed retrospectively.

Results

A total of 30 patients were enrolled, with a male/female ratio of 4:1 and a median age of 42 years. Twenty‐nine patients received chemotherapy, of whom 15 patients received asparaginase‐based (ASP‐based) regimens. Moreover, seven received surgery and three received radiotherapy. The overall response an d complete remission rates were 50.0% and 30.0% for the whole cohort, 50.0% and 37.5% for patients treated with ASP‐based regimens, and 50.0% and 25.0% for those treated with non‐ASP‐based regimens, respectively. The median follow‐up was 12.9 months and the 1‐year overall survival rate was 40.0% for the whole cohort. For those patients in an early stage, ASP‐based regimens resulted in a superior 1‐year progression‐free survival rate compared to non‐ASP‐based regimens (100.0% vs. 36.0%, p = .07). However, ASP‐based regimens did not improve survival in patients at an advanced stage.

Conclusion

GI‐ENKTL still has a poor prognosis, even in the era of modern asparaginase‐based treatment strategies.
Effects of Edge Functionalization of Nanographenes with Small Aromatic Systems
Authors: Takahashi Shusaku , Sekiya Ryo , Haino Takeharu
Published: March 2023

Regulation of the physical properties of nanographenes (NGs) by edge functionalization is an active research area. We conducted a computational study of the effects of edge functionalization on the physical properties of NGs. The computed NGs were models of experimentally obtained NGs and composed of a C174 carbon framework with one to four 3,5‐dimethylnaphthalene units on the edge. The effects were assessed structurally, magnetically, and electronically by the least square planarity index, harmonic oscillator model of aromaticity, nucleus‐independent chemical shift, and HOMO–LUMO (H–L) gaps. Density functional theory calculations indicate that although the structures of the model NGs are not very sensitive to edge functionalization, but the magnetic and electronic properties are. The installed substituents narrowed the H−L gap and induced a redshift of the photoluminescence (PL) band by the π conjugation between NG and the substituent. These results are consistent with the extension of the absorption band and the redshift of the PL bands of the experimentally modified NGs. Furthermore, the calculations confirmed the contribution of the charge transfer character to the absorption spectra.
Association between Life's Essential 8 score and risk of premature mortality in people with and without type 2 diabetes: A prospective cohort study
Authors: Sun Ying , Yu Yuefeng , Zhang Kun , Yu Bowei , Yu Yuetian , Wang Yuying , Wang Bin , Tan Xiao , Wang Yu , Lu Yingli , Wang Ningjian
Published: March 2023

Aims

To evaluate the association of cardiovascular health (CVH), measured by Life's Essential 8 score, with the risk of premature mortality and to determine the patterns of CVH‐related differences in life expectancy among people with and without type 2 diabetes (T2D).

Materials and Methods

This prospective study included 309,789 participants (age 56.6 ± 8.1 years; 46% men) enroled in the UK Biobank. The Life's Essential 8 composite measure consists of four health behaviours (diet, physical activity, nicotine exposure, and sleep) and four health factors (BMI, non‐HDL cholesterol, blood glucose, and blood pressure), and the maximum CVH score was 100 points. CVH was categorised into low, moderate, and high groups. Premature death was defined as death before the age of 75. Cox proportional hazard ratios (HRs) with 95% confidence intervals (CIs) were calculated, and life expectancy was estimated.

Results

During a median follow‐up of 12.7 years, 13,683 cases of premature death were documented. Compared to participants with low CVH, the multivariable HRs (95% CIs) of premature death were 0.59 (0.56–0.62) and 0.42 (0.39–0.45) for the moderate and high CVH groups, respectively. This association was stronger in participants with T2D compared with those without T2D. At the age of 50 years, compared to low CVH groups, high CVH was associated with a gain of 9.79 (9.70–9.87) and 5.58 (5.48–5.67) additional life years for men with and without T2D, respectively. The corresponding life gain for women with and without T2D was 24.21 (24.13–24.27) and 10.18 (10.10–10.27), respectively.

Conclusions

Maintaining an ideal Life's Essential 8 score may provide more benefits for people with T2D than for those without T2D, including a lower risk of premature death and an increased lifespan.
Water availability and seasonality shape elemental stoichiometry across space and time
Authors: Atkinson Carla L. , Shogren Arial J. , Smith Chelsea R. , Golladay Stephen W.
Published: March 2023

The interaction of climate change and increasing anthropogenic water withdrawals is anticipated to alter surface water availability and the transport of carbon (C), nitrogen (N), and phosphorus (P) in river networks. But how changes to river flow will alter the balance, or stoichiometry, of these fluxes is unknown. The Lower Flint River Basin (LFRB) is part of an interstate watershed relied upon by several million people for diverse ecosystem services, including seasonal crop irrigation, municipal drinking water access, and public recreation. Recently, increased water demand compounded with intensified droughts have caused historically perennial streams in the LFRB to cease flowing, increasing ecosystem vulnerability. Our objectives were to quantify how riverine dissolved C:N:P varies spatially and seasonally and determine how monthly stoichiometric fluxes varied with overall water availability in a major tributary of LFRB. We used a long‐term record (21–29 years) of solute water chemistry (dissolved organic carbon, nitrate/nitrite, ammonia, and soluble reactive phosphorus) paired with long‐term stream discharge data across six sites within a single LFRB watershed. We found spatial and seasonal differences in soluble nutrient concentrations and stoichiometry attributable to groundwater connections, the presence of a major floodplain wetland, and flow conditions. Further, we showed that water availability, as indicated by the Palmer Drought Severity Index (PDSI), strongly predicted stoichiometry with generally lower C:N and C:P and higher N:P fluxes during periods of low water availability (PDSI < −4). These patterns suggest there may be long‐term and significant changes to stream ecosystem function as water availability is being dramatically altered by human demand with consequential impacts on solute transport, in‐stream processing, and stoichiometric ratios.
Synthesis and Characterization of New Mononuclear Ru (II) PolypyridylComplexes with Catalytic Activity
Authors: Peyrot Analia Mercedes , Zelaya María Priscila , Alborés Pablo , Fagalde Florencia
Published: March 2023

In this work, we report the synthesis and physicochemical characterization of new chloro and aqua mononuclear Ru (II) complexes of formula [Ru(LLL)(dpp)Cl]PF6and [Ru(LLL)(dpp)OH2](PF6)2(LLL=tpy =2,2’ : 6’,2’’‐terpyridine; tptz=2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine and dpp=2,3‐bis(2‐pyridil)pyrazine). For the complex [Ru(tptz)(dpp)Cl]PF6, the complete structure was determined by X‐ray diffraction. Catalytic studies of aqua‐complexes revealed that they are active for the water oxidation reaction at pH 1 using cerium ammonium nitrate (CAN) as a sacrificial oxidant. Also, we were able to establish the reaction mechanism and rate constants of each stage of the catalytic cycle, turnover frequencies (TOFs), and turnover numberes (TONs). The experimental TON values for the aqua complexes were very close to the theoretical value of 7.5, indicating a high degree of recovery. DFT and TD‐DFT calculations of electronic states for all complexes were consistent with experimental results and allowed the complete assignment of their UV‐Visible bands and redox states.
Syntheses, Structures, and Electronic Properties of Mono‐ and Bimetallic Thiolato Complexes Containing Unusual Coordination Modes of Thiolato Ligands
Authors: Bairagi Subhash , Pradhan Alaka Nanda , Cordier Marie , Roisnel Thierry , Ghosh Sundargopal
Published: March 2023

Synthesis, bonding and chemistry of mono‐ and bimetallic complexes supported by chelating thiolato ligands have been established. Treatment of [Cp*VCl2]3(1) with [LiBH4 ⋅ THF] followed by the addition of ethane‐1,2‐dithiol led to the formation of an EPR active bimetallic vanadium thiolato complex [(Cp*V){μ‐(SCH2CH2S)‐κ2S,S′)2{V(SCH2CH2S‐SH)}] (2). In complex2, two ethane‐1,2‐dithiolato ligands are symmetrically coordinated to two vanadium atoms throughμ‐S atoms. Interestingly, when similar reactions were carried out with heavier group 5 metal precursors, such as [Cp*NbCl4] (3 a), it afforded monometallic thiolato complex [Cp*Nb(SCH2CH2S)(SCH2CH2S−CH2S)] (4 a). On the other hand, the Ta‐analogue [Cp*TaCl4] (3 b) yielded thiolato species [Cp*Ta(SCH2CH2S)(SCH2CH2S−CH2S)] (4 b) and [Cp*Ta(SCH2CH2S) (SCH2CH2S−S)] (5). In complexes4 aand4 b, one ethane‐1,2‐dithiolato and one trithiolato ligand are coordinated to Nb and Ta centers, respectively. Whereas, in complex5, one ethane‐1,2‐dithiolato and one 2‐disulfanylethanethiolato is coordinated to the Ta center. Moreover, the photolytic reaction of5with [Mo(CO)5 ⋅ THF] yielded heterobimetallic thiolato complex [(Cp*Ta){μ‐(SCH2CH2S)‐κ2S,S′}{μ‐(SCH2CH2S−CH2(CH3)S)κ2S′′ : κ1S‐′′′′ : κ1S′′′′′}{Mo(CO)3}] (6). All the complexes have been characterized by multinuclear NMR spectroscopy and single crystal X‐ray diffraction studies. Further, computational analyses were performed to provide an insight into the bonding of these complexes.
Highly Fluorescent 2‐Aminopurine Derivatives: Synthesis, Photo‐physical Characterization, and Preliminary Cytotoxicity Evaluation
Authors: Gonçalves Jorge M. , Gonçalves João N. D. , Pêra Ana S. , Senhorães Nádia R. , Rodrigues Ana Rita O. , Oliveira Rui , Coutinho Paulo J. G. , Castanheira Elisabete M. S. , Dias Alice M.
Published: March 2023

New fluorescent nucleobase analogues (FBAs) are emerging as extraordinarily useful tools for DNA labelling technologies. The highly fluorescent adenine analogue 2‐aminopurine (2AP) is still the most used within the few hundreds of newly FBAs synthesized, but its excitation in the UV region demands for high energy sources endangering living cells. New and highly fluorescent 2AP derivatives, 2‐amino‐6‐cyanopurines, were obtained using simpler but efficient synthesis method. All the new compounds exhibit advantageous photophysical properties over 2AP, showing absorption and emission bands ranging the visible region (blue‐green region), high fluorescence quantum yields and Stokes’ shifts, especially in non‐protic organic solvents. Density Functional Theory calculations (DFT) of electronic and vibrational structure were performed, allowing to predict absorption and emission spectra. In addition, these 2‐amino‐6‐cyanopurines exhibit little to no toxicity in assays using yeast cells.
Tolerability and pharmacokinetics of intravenous allopregnanolone with and without midazolam pretreatment in two healthy dogs
Authors: Bruun Donald A. , Ma Betty , Chen Yi‐Je , Wu Chun‐Yi , Aleman Monica , Zolkowska Dorota , Smiley‐Jewell Suzette M. , Rogawski Michael A. , Lein Pamela J.
Published: March 2023

The neurosteroid allopregnanolone (ALLO) is under investigation as a treatment for benzodiazepine‐refractory status epilepticus (SE). Here, we assess the cardiopulmonary safety of intravenous ALLO by itself and after a clinically recommended dose of midazolam (MDZ) in two healthy adult beagles. Each dog received ALLO (1 mg/kg, IV), and after a washout period of 2 weeks, each dog was dosed with MDZ (0.2 mg/kg, IV) followed 10 minutes later by ALLO. Behavioral state, vital signs, arterial blood gases, blood chemistries, and plasma ALLO concentrations were monitored for up to 6 hours after dosing. The dogs appeared sleepy but were fully responsive after both treatments. No depression of mean arterial pressure or respiratory rate was noted. Blood gas measurements failed to show evidence of drug‐induced acute respiratory acidosis. Estimated maximum plasma ALLO concentrations were in the range of 1500 to 3000 ng/ml. The results indicate that intravenous ALLO can be used safely to treat benzodiazepine‐refractory SE, even when administered shortly after a benzodiazepine.
Validation of Nickel Bioavailability Models for Algae, Invertebrates, and Fish in Chinese Surface Waters
Authors: He Jia , Wang Cheng , Schlekat Christian E. , Wu Fengchang , Middleton Elizabeth , Garman Emily , Peters Adam
Published: March 2023

Nickel (Ni) is used primarily in the production of alloys like stainless steel and is increasingly being used in the production of batteries for the electric vehicle market. Exposure of Ni to ecosystems is of concern because Ni can be toxic to aquatic organisms. The influence of water chemistry constituents (e.g., hardness, pH, dissolved organic carbon) on the toxicity of Ni has prompted the development and use of bioavailability models, such as biotic ligand models (BLMs), which have been demonstrated to accurately predict Ni toxicity in broadly different ecosystems, including Europe, North America, and Australia. China, a leading producer of Ni, is considering bioavailability-based approaches for regulating Ni emissions. Adoption of bioavailability-based approaches in China requires information to demonstrate the validity of bioavailability models for the local water chemistry conditions. The present study investigates the toxicity of Ni to three standard test species (Daphnia magna, Pseudokirchneriella subcapitata, and Danio rerio) in field-collected natural waters that are broadly representative of the range of water chemistries and bioavailabilities encountered in Chinese lakes and rivers. All experimental data are within a factor of 3 of the BLM predicted values for all tests with all species. For D. magna, six of seven waters were predicted within a factor of 2 of the experimental result. Comparison of experimental data against BLM predictions shows that the existing Ni bioavailability models are able to explain the differences in toxicity that result from water chemistry conditions in China. Validation of bioavailability models to water chemistries and bioavailability ranges within China provides technical support for the derivation of site-specific Ni water quality criteria in China. Environ Toxicol Chem 2023;42:1257–1265. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Ecological Harm and Economic Damages of Chemical Contamination to Linked Aquatic-Terrestrial Food Webs: A Study-Design Tool for Practitioners
Authors: Kraus Johanna M. , Skrabis Kristin , Ciparis Serena , Isanhart John , Kenney Aleshia , Hinck Jo Ellen
Published: March 2023

Contamination of aquatic ecosystems can have cascading effects on terrestrial consumers by altering the availability and quality of aquatic insect prey. Comprehensive assessment of these indirect food-web effects of contaminants on natural resources and their associated services necessitates using both ecological and economic tools. In the present study we present an aquatic-terrestrial assessment tool (AT2), including ecological and economic decision trees, to aid practitioners and researchers in designing contaminant effect studies for linked aquatic-terrestrial insect-based food webs. The tool is tailored to address the development of legal claims by the US Department of the Interior's Natural Resource Damage Assessment and Restoration Program, which aims to restore natural resources injured by oil spills and hazardous substance releases into the environment. Such cases require establishing, through scientific inquiry, the existence of natural resource injury as well as the determination of the monetary or in-kind project-based damages required to restore this injury. However, this tool is also useful to researchers interested in questions involving the effects of contaminants on linked aquatic-terrestrial food webs. Stylized cases exemplify how application of AT2 can help practitioners and researchers design studies when the contaminants present at a site are likely to lead to injury of terrestrial aerial insectivores through loss of aquatic insect prey and/or dietary contaminant exposure. Designing such studies with ecological endpoints and economic modeling inputs in mind will increase the relevance and cost-effectiveness of studies, which can in turn improve the outcomes of cases and studies involving the ecological effects of contaminants on food webs. Environ Toxicol Chem 2023;42:2029–2039. Published 2023. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Facile Bond Activation of Small Molecules by an Acyclic Imino(silyl)silylene
Authors: Zhu Huaiyuan , Hanusch Franziska , Inoue Shigeyoshi
Published: March 2023

The activation of small molecules by silylenes bearing unique electronic properties has been well established in the past few decades. Here, we disclose the reactivity study of acyclic imino(silyl)silylene 1 with an N‐heterocyclic imine ligand (NHI) towards various small molecules. Silylene 1 undergoes facile activation of gaseous molecules like dihydrogen, ethylene, and carbon dioxide. While the cycloaddition of carbonyl compounds to 1 was shown as a straightforward synthetic approach of oxasilacycles, reaction with silane as well as borane led to the corresponding E−H (E=Si, B) insertion products. Moreover, reaction with heavier chalcogens allow the isolation of neutral three‐coordinate silicon‐heavier chalcogen double bond complexes.
Modified Periodic Acid‐Schiff (PAS) Is an Alternative to Safranin O for Discriminating Bone–Cartilage Interfaces
Authors: Kjosness Kelsey M , Reno Philip L , Serrat Maria A
Published: March 2023

Cartilage histomorphometry is often performed on decalcified, paraffin‐embedded bone sections, which provide versatility in staining applications from basic morphology to immunohistochemistry. Safranin O is a cationic dye that binds to proteoglycans in cartilage and is routinely used to assess growth plate dynamics and/or fracture repair at bone–cartilage interfaces. When used with a counterstain such as fast green, safranin O can offer exquisite differentiation of cartilage from surrounding bone. However, various decalcification and processing methods can deplete proteoglycans, rendering inconsistent, weak, or absent safranin O staining with indiscriminate bone–cartilage boundaries. We sought to develop an alternative staining methodology that preserves the contrast of bone and cartilage in cases of proteoglycan depletion that can be applied when other cartilage stains are unsuccessful. Here, we describe and validate a modified periodic acid‐Schiff (PAS) protocol that we developed using Weigert's iron hematoxylin and light green stains as an alternative to safranin O for discriminating bone–cartilage interfaces of skeletal tissues. This method provides a practical solution for differentiating bone and cartilage when safranin O staining is not detected after decalcification and paraffin processing. The modified PAS protocol can be useful for studies in which identification of the bone–cartilage interface is essential but may not be preserved with standard staining approaches. © 2023 The Authors. JBMR Plus published by Wiley Periodicals LLC on behalf of American Society for Bone and Mineral Research.
Pharmacognostical evaluation and physiochemical analysis ofSalsola Kalias medicinal plant
Authors: Hameed Aiza , Ghani Nadia , Mughal Tahira Aziz , Abbas Moneeza , Abrar Amina , Javed Houda
Published: March 2023

One of the largest genera Salsola include halophytic plants with therapeutic potential. For the treatment of various ailments, plants of the genus are acclaimed.Salsola kaliis an important medicinal plant exhibiting specific phytochemical and biological makeup that is frequently overlooked. The current study aimed at the pharmacognostical evaluation of leaves and stem ofSalsola kalito ensure the purity, quality, and efficacy of this valuable medicinal species. For the identification, evaluation and standardization of diagnostic attributes of intact and powdered material ofSalsola kalileaves and stem, various methods including organoleptic, macroscopic, microscopic, and physicochemical analysis were employed. The plant was identified to possess significant characteristics with a view to authenticate drug. Light Microscopy (LM) and Scanning Electron Microscopy (SEM) of aerial parts ofSalsola kalimanifested specialized anatomical features essential for the adaptability in dry‐saline environment. Upon quantitative pharmacognostic analysis of powder of leaves and stem, the moisture content of 1.3% and 11.1%, respectively was found. The total ash (%) in leaves and stem was computed to be 65.95 and 85.3, respectively. The water soluble and alcohol soluble extractive values (%) were computed to be 79.38 and 75.4 in leaves and 78.0 and 76.8 in stem, respectively. The swelling index (cm) in leaves and stem was enumerated to be 0.8 and 0.5. The current study will be helpful in the quality check and authentication of various parts ofSalsola kalithat can be used as principal component of herbal medicine formulation.

Based on various microscopic analyses, that is, Light Microscopy and Scanning Electron Microscopy, the detailed description and valuable information onSalsola kali, a medicinal plant, has been provided.

The present study can make a significant contribution in the literature as the findings may contribute to the determination of purity ofSalsola kalifor future perspectives.
Application of the network scale‐up method to estimate the sizes of key populations for HIV in Singapore using online surveys
Authors: Quaye Sharon Esi Duoduwa , Cheng Yuwei , Tan Rayner Kay Jin , Koo Joel R. , Prem Kiesha , Teo Alvin Kuo Jing , Cook Alex R.
Published: March 2023

Introduction

Singapore lacks robust data on the sizes of the key populations that are most at risk for HIV. Using the network scale‐up method for hidden or hard‐to‐reach populations, we estimate the sizes of five key populations—male clients of female sex workers (MCFSW), men who have sex with men (MSM), female sex workers (FSW), people who inject drugs (PWID) and transgender people—and profile the ages and ethnicities of respondents with the high‐risk contacts they report knowing.

Methods

We conducted a cross‐sectional online survey between March and May 2019 (n = 2802) using a network scale‐up instrument previously developed for Singapore. Participants were recruited using an existing panel and online advertising, and the sample reweighted by age, sex, ethnicity and education attained to represent the general adult population. We built a Bayesian hierarchical model to estimate the sizes of the five key populations for HIV in Singapore.

Results

After adjustment, the sizes of the at‐risk populations are estimated to be: 76,800 (95% credible interval [CI]: 64,200–91,800) MCFSW; 139,000 (95% CI: 120,000–160,000) MSM; 8030 (95% CI: 3980–16,200) FSW; 3470 (95% CI: 1540–7830) PWID and 18,000 (95% CI: 14,000–23,200) transgender people. Generally, men reported knowing more people in all the high‐risk groups; older people reported knowing more MCFSW, FSW and transgender people; and younger people reported knowing more MSM. There was a bimodal effect of age on those who reported knowing more PWIDs: people in their 20s and 60s reported more contacts.

Conclusions

This study demonstrates that a size estimation study of hidden populations is quickly and efficiently scalable through using online surveys in a socially conservative society, like Singapore, where key populations are stigmatized or criminalized. The approach may be suitable in other countries where stigma is prevalent and where barriers to surveillance and data collection are numerous.
Altered gut microbiota is associated with different immunologic responses to antiretroviral therapy in HIV‐infected men who have sex with men
Authors: Zhao Heping , Feng Anping , Luo Dan , Wu Hao , Zhang Ge , Zhang Lin , Yuan Jinqiu , Lin Yi‐Fan , Li Linghua , Zou Huachun
Published: March 2023

The association between gut microbiota and immunologic nonresponse among people living with HIV (PLHIV) on antiretroviral therapy (ART) is not well documented. This study aimed to characterize gut microbiota among HIV‐infected men who have sex with men (MSM) with different immunologic responses. We recruited HIV‐infected MSM and HIV‐uninfected MSM (healthy controls, HC) in Guangzhou, June–October 2021. HIV‐infected MSM were grouped into good immunological responders (GIR) (CD4 + T cell count ≥ 350 cells/μL) and poor immunological responders (PIR) (<350 cells/μL). Blood and stool samples were collected. Microbial translocation in serum was performed using enzyme‐linked immunosorbent assay (ELISA). Bacterial 16S ribosomal DNA sequencing was performed on stool samples, and microbial metabolites were obtained through gas chromatography‐mass spectrometry. 56 GIR, 41 PIR, and 51 HC were included. Microbial translocation marker soluble cluster of differentiation 14 (sCD14) in both GIR and PIR groups was significantly higher than that in HC. Compared with PIR or HC groups, the genera of Coprococcus, Blautia, Clostridium, and SMB53 were decreased, whereas Megamonas and Megasphaera were more abundant in GIR group. Compared with GIR or PIR groups, Bifidobacterium, Collinsella, Faecalibacterium, Oscillospira, and Roseburia were more abundant, whereas Escherichia was decreased in HC group. The levels of benzenoids, imidazoles, phenylpropanoic acids, phenylpropanoids, and pyridines showed strongly significant correlations between differential genera. This study presented a comprehensive landscape of gut microbiota in PLHIV with different treatment outcomes. Megamonas, Coprococcus and Blautia were the major genera correlated with different immunologic responses in PLHIV.
Sulfolipid substitution ratios of Microcystis aeruginosa and planktonic communities as an indicator of phosphorus limitation in Lake Erie
Authors: Martin Robbie M. , Denney Maddie K. , Pound Helena L. , Chaffin Justin D. , Bullerjahn George S. , McKay R. Michael L. , Zastepa Arthur , Jones Katarina A. , Castro Hector F. , Campagna Shawn R. , Wilhelm Steven W.
Published: March 2023

Phosphorus (P) availability frequently limits primary production in lakes, influences the physiology of phytoplankton, shapes community structure, and can stimulate or constrain the formation of cyanobacterial blooms. Given the importance of P, numerous methods are available to assess P stress in phytoplankton communities. Marine phytoplankton are known to substitute sulfolipids for phospholipids in response to P limitation. We asked whether sulfolipid substitution might serve as an additional indicator of P stress in freshwater phytoplankton communities. The question was addressed using cultures of Microcystis aeruginosa, Lake Erie microcosms, and surveys of lipid profiles in Lake Erie during a Microcystis spp. bloom. Peak area response ratios of the intact polar lipids sulfoquinovosyldiacylglycerol (SQDG) to phosphatidylglycerol (PG) were used as the metric of lipid substitution. In cultures of M. aeruginosa NIES‐843, the SQDG : PG ratio increased from ~ 0.9 to ~ 3.3 with decreasing P concentration. In P‐limited communities, the SQDG : PG ratio increased from ~ 6 to ~ 11 after 48 h in microcosm controls, while P amendments reduced the ratio to ~ 3. In Lake Erie surveys, the SQDG : PG ratio ranged from ~ 0.4 to ~ 7.4 and was negatively correlated (Pearson r = −0.62) with total dissolved P. The SQDG : PG ratio was not correlated with concentrations of chlorophyll a, soluble reactive P, or N : P molar ratios. These results demonstrated that M. aeruginosa and Microcystis‐dominated communities remodel lipid profiles in response to P scarcity, providing a potential short‐term, time‐integrated biomarker of nutrient history and P stress in fresh waters.
Fluorous Tagged Peptides for Intracellular Delivery and Biomedical Imaging
Authors: Ding Lei , Rong Guangyu , Cheng Yiyun
Published: March 2023

Fluorous tagged peptides have shown promising features for biomedical applications such as drug delivery and multimodal imaging. The bioconjugation of fluoroalkyl ligands onto cargo peptides greatly enhances their proteolytic stability and membrane penetration via a proposed “fluorine effect”. The tagged peptides also efficiently deliver other biomolecules such as DNA and siRNA into cells via a co‐assembly strategy. The fluoroalkyl chains on peptides with antifouling properties enable efficient gene delivery in the presence of serum proteins. Besides intracellular biomolecule delivery, the amphiphilic peptides can be used to stabilized perfluorocarbon‐filled microbubbles for ultrasound imaging. The fluorine nucleus on fluoroalkyls provides intrinsic probes for background‐free magnetic resonance imaging. Labeling of fluorous tags with radionuclide 18F also allows tracing the biodistribution of peptides via positron emission tomography imaging. This mini‐review will discuss properties and mechanism of the fluorous tagged peptides in these applications.
Nanobiotechnology‐mediated radioimmunotherapy treatment for triple‐negative breast cancer
Authors: Zhu Mei , Yang Xi , You Jia , Zheng Lingnan , Yi Cheng , Huang Ying
Published: March 2023

Breast cancer has become the most common and greatest threat to women's health in the world. As the most dangerous subtype of breast cancer, triple‐negative breast cancer (TNBC) can lead develop drug resistance, resulting in poor therapeutic effects. The synergistic effect of radiotherapy and immunotherapy can not only improve the therapeutic effect of in situ TNBC but also induce the strong abscopal effect of radiotherapy to remove the tumor cells from the metastatic tumor and prevent tumor recurrence. However, many preclinical studies have pointed out that the application of radioimmunotherapy still has such problems as large toxic and side effects of drugs and asynchronous administration scheme. With the increasing popularity of nanobiotechnology in tumor therapy, there are more and more research results related to nanoparticles, such as inorganic nanoparticles, organic nanoparticles, and nanoparticle–hydrogel complexes in radioimmunotherapy. In this review, we briefly summarize the related clinical treatment methods of TNBC and review the related nanobiotechnology used in the preclinical studies of TNBC radioimmunotherapy. It is mainly characterized by the controlled release of drugs locally, enhanced radiosensitization, and avoidance of systemic toxicity. However, further studies are needed to improve the convenience and effectiveness, so as to explore new options for the clinical treatment of TNBC.
The rapid rise of SARS‐CoV‐2 Omicron subvariants with immune evasion properties: XBB.1.5 and BQ.1.1 subvariants
Authors: Ao Danyi , He Xuemei , Hong Weiqi , Wei Xiawei
Published: March 2023

As the fifth variant of concern of the SARS‐CoV‐2 virus, the Omicron variant (B.1.1.529) has quickly become the dominant type among the previous circulating variants worldwide. During the Omicron wave, several subvariants have emerged, with some exhibiting greater infectivity and immune evasion, accounting for their fast spread across many countries. Recently, two Omicron subvariants, BQ.1 and XBB lineages, including BQ.1.1, XBB.1, and XBB.1.5, have become a global public health issue given their ability to escape from therapeutic monoclonal antibodies and herd immunity induced by prior coronavirus disease 2019 (COVID‐19) vaccines, boosters, and infection. In this respect, XBB.1.5, which has been established to harbor a rare mutation F486P, demonstrates superior transmissibility and immune escape ability compared to other subvariants and has emerged as the dominant strain in several countries. This review provides a comprehensive overview of the epidemiological features, spike mutations, and immune evasion of BQ.1 and XBB lineages. We expounded on the mechanisms underlying mutations and immune escape from neutralizing antibodies from vaccinated or convalescent COVID‐19 individuals and therapeutic monoclonal antibodies (mAbs) and proposed strategies for prevention against BQ.1 and XBB sublineages.
Optimal tracking control for blast furnace molten iron quality based on subspace identification and Krotov's method
Authors: Liu Yue , Zhou Ping
Published: March 2023

Blast furnace ironmaking is a complex nonlinear dynamic process, which has strict requirements on the quality of final molten iron. To improve the control effect of molten iron quality, this paper proposes an optimal tracking control method for molten iron quality based on the bilinear subspace identification and Krotov's method. First, a state space model between key process variables and blast furnace molten iron quality, using the bilinear subspace identification method, is established based on actual industrial data. Then, an augmented system is established combining the state vector and the reference trajectory, and the improving feedback controller is designed by solving a set of Riccati equations, which are established based on Krotov's method. In combination with the designed controller and the established system, the specific implementation steps are proposed. Finally, the effectiveness and advancement of the proposed method are verified based on actual industrial data of a large blast furnace.
Ductus arteriosus flow predicts outcome in neonates with congenital diaphragmatic hernia
Authors: Bo Bartolomeo , Pugnaloni Flaminia , Licari Amelia , Patel Neil , Strizek Brigitte , Lemloh Lotte , Leyens Judith , Mueller Andreas , Kipfmueller Florian
Published: March 2023

Objective

To investigate whether the pattern of flow through the ductus arteriosus (DA) is associated with the need for extracorporeal membrane oxygenation support (ECMO) or death in neonates with congenital diaphragmatic hernia (CDH).

Design

Retrospective observational study.

Setting

German level III Neonatal Intensive Care Unit.

Participants

139 CDH neonates were born between March 2009 and May 2021.

Methods

DA flow pattern was assessed in echocardiograms obtained within 24 h of life by measuring flow time and velocity time integral (VTI) for both left‐to‐right (LR) and right‐to‐left (RL) components of the ductal shunt. A VTI ratio (VTILR/VTIRL) < 1.0 and an RL relative flow time (Flow timeRL/(Flow timeLR+Flow timeRL)) >33% were defined as markers of abnormal flow patterns. The primary outcome was the need for ECMO. The secondary outcome was death.

Results

72 patients (51.8%) had a VTI ratio <1.0, 73 (52.5%) an RL relative flow time >33%. 59 patients (42.4%) had an alteration of both values. Need for ECMO was present in 37.4% (n = 52), while 19.4% (n = 27) died. A VTI ratio <1.0 had the highest diagnostic accuracy for the need for ECMO, (sensitivity 82.7%, specificity 66.7%, negative predictive value [NPV] 86.6%, and positive predictive value [PPV] 59.7%) as well as for death (sensitivity 77.8%, specificity 54.5%, NPV 91.0%, and PPV 29.2%). Patients with VTI ratio <1.0 were 4.7 times more likely to need ECMO and 3.3 times more likely to die. VTI ratio values correlated significantly with pulmonary hypertension (PH) severity (r = ‐0.516, p < 0.001).

Conclusions

A VTI ratio <1.0 is a valuable threshold to identify high‐risk CDH neonates. For improved risk stratification, other parameters—for example, left ventricular cardiac dysfunction—should be combined with DA flow assessment.