bluuebunny/crossref_metadata_2025 huggingface dataset:
Suburban Tourism Market in Canggu, Bali
Authors: Adikampana I. Made
Published: March 2022

Canggu is a village adjacent to Kuta as a strategic tourism area and the core urban area of Metropolitan Sarbagita. This position has an impact on the massive spatial change of agriculture into tourism and settlements. The change indicates that Canggu is undergoing a suburbanization process. This study aims to identify the characteristics of tourists in the suburban area of Canggu. The survey method was utilized to achieve these objectives. The tourist survey is used to collect data on the profile of the tourism market from May to June 2021. The data is processed with simple statistics and then analyzed descriptively to provide guidance for the development of tourism products in the suburban area of Canggu. The results showed that during this pandemic the Canggu tourism market was dominated by local tourists with the following characteristics: staying for a long time; prefer villas and hotels as accommodation; the plethora of millennials and generation Z; self-employed work with the flexibility of time and money arrangements; highly educated; the spending power of tourism products is high, especially for accommodation and consumption. With these characteristics, local tourist position is very important in the context of developing tourism products, not only during a pandemic but also predictably in a sustainable manner. Two guidance for the development of sustainable tourism products can be recommended in the suburban area of Canggu: 1) promoting homestays and local culinary facilities and 2) creating a variety of activities to maintain and increase the length of stay of tourists in suburban areas.
Impact of Corporate Diversification on Sustainability of Listed Health Care Firms in Nigeria
Authors: Emeka Omaliko , Ngozi Okpala
Published: March 2022

This study was carried out on impact of corporate diversification on the sustainability of healthcare companies in Nigeria. To determine the relationship between corporate diversification and organizational sustainability, corporate diversification was measured using geographic diversification (GEODIV), operational diversification (OPDIV), and product diversification (PRODIV), while sustainability, on the other hand, was measured using Kinder Lydenberg Domini (KLD) rating system on social-environmental performance. Ex post facto design was used and the data were collected from the annual reports and accounts of the listed healthcare companies in Nigeria for the period up to 2016-2020. The OLS model was used in the data analysis and the results of the study show that geographic diversification, operational diversification & product diversification have positive and a significant effect on corporate sustainability at a significant level of 1%. Therefore, the study concluded that corporate diversification ensures organizational sustainability in Nigeria. Hence, the study recommended that business organizations should engage in diversification (GEODIV, OPDIV & PRODIV) as this ensures organizational sustainability. Hence, proper management of diversification decisions is required, as over-diversification could lead to a deterioration in the company's financial performance.
Effect of Rainfall Variability on Groundwater Levels in Nzoia River Basin, Kenya
Authors: Odwori Ernest Othieno
Published: March 2022

Groundwater is a critical supply of freshwater in Africa, providing safe drinking water near to where it is needed for homes, agricultural, and industrial uses. Due to the high vulnerability of surface water resources to anthropogenic activities and climate change, groundwater consumption has increased dramatically over the last 50 years and is likely to continue rising in future. This study examines the effect of rainfall variability on groundwater levels using rainfall and groundwater level fluctuation data from Nzoia River Basin, Kenya. A cross-sectional survey design was used. Three counties were randomly selected from the basin for study with Busia representing the lower catchment, Kakamega middle catchment and Trans Nzoia upper catchment. Groundwater is the main drinking water resource in the basin supplying 78.8% of the population. Knowledge of long-term rainfall variability and the associated response of the basin’s groundwater resources are essential for efficient and sustainable groundwater management.  Despite the relatively short period for which water level records are available, these records contain valuable information that can be used beneficially in the development of strategies to assist in the responsible management of our limited groundwater resources. Rainfall and groundwater levels were analysed using the parametric test of linear regression and the non-parametric Mann–Kendall statistical test. Rainfal data for this study was obtained from the Kenya Meteorological Department (KMD) and the Groundwater levels from Kenya Water Resources Management Agency (WRMA). Pearson moment correlation was used to check the relationship between monthly rainfall and monthly groundwater levels. Correlations between groundwater levels and rainfall will help assess aquifer vulnerability to climate change in the basin. Our results indicate that rainfall variability induced by climate change has greatly impacted groundwater levels in the basin. Annual groundwater levels have been steadly falling at the rate between 0.03 ft/year (Kakamega Tande School) and 0.49 ft/year (Kitale Golf Club) in the basin. Annual rainfall over the basin has shown stations recording both decreasing and increasing trends. The falling groundwater level trends indicate a cause for concern and provide a scientific basis for the national and county governments in the basin to strategize on ground water development and management for sustainable water use.
Important Atmospheric Parameters over a Indian Tropical Station Using Various Remote Sensing Instruments and a Model
Authors: Sreedevi S. , Brahmanandam P. S. , Rao K. Tarakeswara , Kumar V. Naveen , Kumar G. Anil , Samatha K. , Rao M. P.
Published: March 2022

For the periods 01 July, 02 July, and 03 July 2018, important atmospheric parameters such as temperature, relative humidity, pressure, wind direction, and wind speed have been calculated over a tropical Indian station Gadanki (13.5°N, 79.2°E). Atmospheric Boundary Layer height (ABLH) was estimated using various analytical methods such as, vertical gradient, double gradient, and logarithmic gradient, and the results are compared with the European Centre for Medium-Range Weather Forecasts (ECMWF) ABLH data. With the COSMIC Radio Occultation (RO) technique and a regular balloon-borne radiosonde, tropopause heights and their corresponding temperatures were determined using minimum temperature criteria. Gradient and double gradient methods were more successful at capturing ABLHs than the logarithmic gradient method.
Outcome of Neonates Born through Meconium Stained Amniotic Fluid in a Tertiary Care Hospital, PAK Emirates Military Hospital Rawalpindi, Pakistan
Authors: Ullah Saeed , Tariq Nadeem Muhammad , Jamal Bakth , Alam Ikram , Qasim Khan Muhammad , Ullah Kiramat , Ahmad Khalil
Published: March 2022

Objective: The study was conducted on the incidence of meconium aspiration syndrome which is still high in the developing world and contributing significantly to the neonatal mortality. The study was aimed to know the risk factors contributing to meconium aspiration syndrome and neonatal outcome in a tertiary hospital (Punjab) Department of pediatric Medicine PAK Emirates Military hospital Rawalpindi in the Pakistan.

Materials and Methods: It was a hospital based cross sectional study This descriptive case series was carried at Department of Peadiatric Medicine PAK Emirates Military hospital Rawalpindi in the Pakistan over a period of one year, from Jan 2019 to Dec 2020, involving 2820 patients; All live newborns born through meconium-stained liquor were enrolled and all the details regarding the mother and neonate were recorded. Odd’s ratio and bivariate analysis was done to assess the risk factors for meconium aspiration syndrome.

Results: Out of all the deliveries 12.4% were born through meconium-stained amniotic fluid and meconium aspiration syndrome developed in 5 .6% of the neonates. Low Apgar score and premature rupture of membranes was significantly associated with the risk of occurrence of meconium aspiration syndrome. Neonates who developed meconium aspiration syndrome had mortality of 6.7%

Conclusion: The Perinatal asphyxia and premature rupture of membranes were significantly associated with the development of meconium aspiration syndrome and neonates who developed meconium aspiration syndrome had high mortality.
Clinicopathologic Predictors of Pathologic Complete Response after Neoadjuvant Systemic Therapy and Impact on Surgical Management
Authors: Niaz Rabia , Soomro Rufina
Published: March 2022

Neoadjuvant systemic therapy previously given for inoperable breast cancer is increasingly being administered in early breast cancer especially in triple negative and HER2 positive molecular subtypes. It is associated with an increased rate of complete pathologic response (PCR) which is a surrogate marker for good survival outcomes and has role in de escalation of surgical management.  We conduct this study to identify clinical and pathologic factors and systemic treatment regimens that predict PCR among Pakistan’s breast cancer patients and its impact on surgical management.

Materials and Methods: Patients with clinical stage I-III who received Neoadjuvant systemic therapy (NST) and underwent surgical intervention at Liaquat national hospital were included. The clinicopathologic factors included age, menopausal status, clinical tumor size, nodal status, stage, pathologic type, grade, molecular subtype, PR status, pathologic response, and treatment in terms of systemic therapy. The surgery underwent and pathologic stage(ypTN) were recorded. The association between these factors and PCR was analyzed with the chi-square test. Univariate analysis was performed to evaluate the influence of clinicopathologic factors on PCR.

Results: PCR was achieved in 174(19.6%) out of the 889 patients. There was a significant association (P-value <0.001) with molecular subtype as follows PCR percentage for HER 2 enriched-39% and luminal B HER 2 positive-31%, triple negative-25% ,Luminal A-6.5% and Luminal B-9.6%, progesterone receptors negative tumors (PCR-26.9%) and chemotherapy regime-Anthracycline and taxane PCR-28%. The predictive value of the three factors remains significant on univariate analysis. The breast conservative surgery rate was 34%, sentinel node biopsy was 60% and axillary PCR is seen in 20% of the patients (cN+ 60% to ypN+ 40%).

Conclusion: NST has a good overall impact in terms of achieving PCR and downsizing for breast-conserving surgery with better cosmetic outcome and de-escalation of axillary surgery. The positive predictive factors include molecular subtype, Her2 positive tumors being the most sensitive, progesterone receptor-negative tumors, and anthracycline and taxane-based chemotherapy.
Blotting Paper for Bench Type Testing - A 48-inch Pilot Paper Machine Production Run
Authors: Dölle Klaus
Published: March 2022

Paper manufacturing originated in China in 105 BC and has come a long way. Countless different paper grades have been developed and are being used all over the world today. One of these paper grades is blotting paper, first recognized in 1465 and machine manufactured in the 1800’s. Today, one of the blotting paper applications is to absorb water during handsheet forming for paper testing.

Blotting paper product with an oven dry basis weight of 269.8 g/m² and 322.6 g/m², a thickness of 484 µm and 566 µm, respectively was manufactured on a 48-inch small commercial Fourdrinier paper machine.

The wet tensile index and stretch was 0.9 Nm/g and 3.54% and 0.94 and 4.04% for the lower and higher bases weight. Water absorbance achieved values of 44.42 mL/s for the top side and 25.43 mL/s for the wire side for the 269.8 g/m² blotting paper and 27.91 for the top side and 20.55 mL/s for wire side of the 322.6 g/m² blotting paper. The minimum total absorbency requirements of 500 ± 50 g/m² was achieved for both basis weights.

Optical properties measured included Opacity at 99.98%, brightness at 86.89%, whiteness at 76.04% and color of 96.43% for the L* value, -0.93 for the a* value, and 3.33 for the b* value.

The manufactured blotting paper has been successfully used producing handsheets with basis weights between 20 g/m² and 300 g/m² utilizing virgin and recycled fiber material.
The use of the Ml flow test between newly diagnostic leprosy cases and in-home contacts / O uso do teste Ml flow entre casos de hanseníase recém-diagnosticados e contatos intradomiciliares
Authors: Da Silva Beatriz Aguiar , De Sousa Gleciane Costa , Moura Maria Edileuza Soares
Published: March 2022

Objetivo: identificar o resultado de teste Ml Flow entre casos de hanseníase recém-diagnosticados e contatos intradomiciliares. Método: estudo transversal, descritivo, com abordagem quantitativa realizado no município de Caxias, Maranhão, Brasil, onde recrutou-se casos recém-diagnosticados, virgens de tratamento e contatos intradomiciliares. Os participantes foram submetidos ao exame dermatológico, neurológico e ao teste Ml Flow, bem como os casos de hanseníase foram submetidos a baciloscopia do raspado intradérmico. Resultados: nos casos recém-diagnosticados o teste Ml Flow foi negativo em 87,5% (7/8) dos paucibacilares e positivo em 70% (21/30) dos multibacilares, ambos concordantes com a baciloscopia do raspado intradérmico. Identificou-se 30 (9%) contatos intradomiciliares com alto risco de adoecer. Conclusão: o teste Ml Flow constitui-se uma ferramenta útil para correta detecção de contatos com alta chance de adoecer da hanseníase, bem como para classificar corretamente os casos novos.
Spectral Shift in the Hydrogen Bonding Peak to Quantify Interfacial Interactions at Polymer/Solid Interfaces
Authors: Singla Saranshu , Dhinojwala Ali
Published: March 2022

Polymer interfaces control many properties such wetting, adsorption, adhesion, friction, and mechanical properties, and understanding interfacial interactions has remained of central importance for years. In this chapter, we discuss the measurements of interfacial interactions (van der Waals and ”polar” acid–base) by measuring shifts in hydrogen bonding peaks using interface‐sensitive sum frequency generation spectroscopy (SFG). We discuss examples that demonstrate the strength of the interfacial interactions (evaluated using spectroscopic shifts) and how it influences polymer adsorption from solutions, segregation from polymer blends, and durability and adhesion strength of coatings and adhesives. A comprehensive understanding of this connection between molecular‐level interactions and macroscopic observables would benefit the design of polymers for targeted applications.
Biden supports treatment, recovery and prevention
Authors: Knopf Alison
Published: March 2022

President Biden's first State of the Union (SOTU) message last week held promise for treatment, including support of the workforce, and hope and support for patients in recovery.
On the Impact of Additive Manufacturing Processes on the Microstructure and Magnetic Properties of Co–Ni–Ga Shape Memory Heusler Alloys
Authors: Scheibel Franziska , Lauhoff Christian , Riegg Stefan , Krooß Philipp , Bruder Enrico , Adabifiroozjaei Esmaeil , Molina-Luna Leopoldo , Böhm Stefan , Chumlyakov Yury I. , Niendorf Thomas , Gutfleisch Oliver
Published: March 2022

Microstructure design allows to prevent intergranular cracking and premature failure in Co–Ni–Ga shape memory alloys. Favorable grain boundary configurations are established using additive manufacturing techniques, namely, direct energy deposition (DED) and laser powder bed fusion (L‐PBF). L‐PBF allows to establish a columnar grain structure. In the Co–Ni–Ga alloy processed by DED, a microstructure with strong ⟨001⟩ texture is obtained. In line with optimized microstructures, the general transformation behavior is essential for performance. Transition parameters such as transition temperature and thermal hysteresis depend on chemical composition, homogeneity, and presence of precipitates. However, these parameters are highly dependent on the processing method used. Herein, the first‐order magnetostructural transformation and magnetization properties of Co–Ni–Ga processed by DED and L‐PBF are compared with single‐crystalline and as‐cast material. In the alloy processed by L‐PBF, Ga evaporation and extensive formation of the ferromagnetic Co‐rich γ'‐phase are observed, promoting a very wide transformation range and large thermal hysteresis. In comparison, following DED, the material is characterized by minor chemical inhomogeneity and transition and magnetization behavior being similar to that of a single crystal. This clearly renders DED‐processed Co–Ni–Ga to become a promising candidate material for future shape memory applications.
Intracellular Self‐Assembly Driven Nucleus‐Targeted Photo‐Immune Stimulator with Chromatin Decompaction Function for Robust Innate and Adaptive Antitumor Immunity
Authors: Zhao Xiu , Zhang Kaixiang , Wang Yiyang , Jiang Wenxiao , Cheng Hui , Wang Qiongwei , Xiang Tingting , Zhang Zhenzhong , Liu Junjie , Shi Jinjin
Published: March 2022

Efficient nuclear DNA damage and release is highly recommended to improve the photodynamic immunotherapy by eliciting innate immune response yet remains challenging. Herein, an intracellular self‐assembly driven nucleus‐targeted photo‐immune stimulator (PIS) with chromatin decompaction function is reported for innate and adaptive antitumor immunity co‐activation. The PIS consists of vorinostat (SAHA)‐loaded manganese‐porphyrin metal‐organic framework (Mn (III)‐TCPP MOF) with further modification of AS1411 aptamer. The PIS can be efficiently internalized by tumor cells and disassembled under the intracellular overexpressed glutathione (GSH). Notably, the released AS1411 is able to be self‐assembled with photosensitizer TCPP in situ within cells, driving nucleus‐targeted delivery of TCPP; meanwhile, the loaded SAHA can induce chromatin decompaction, cooperatively promoting TCPP‐mediated photodynamic nuclear DNA damage and cytosolic release under laser irradiation. In addition, the released manganese ions (Mn2+) further enhance the cytosolic DNA/cyclic GMP‐AMP synthase (cGAS)‐stimulator of interferon gene (STING) pathway mediated innate immunity, which synergizes with PDT‐induced immunogenic cell death to achieve co‐activation of innate and adaptive immunity. Compared to traditional PDT, the self‐assembly driven nucleus‐targeted PDT system with chromatin decompaction show significantly enhanced efficacy for inhibiting primary tumor growth and distant metastasis in several xenograft tumor models, mechanistically by promoting the maturation of dendritic cells and tumor infiltration of natural killer cell, cytotoxic T lymphocytes.
Versatile Phenol‐Incorporated Nanoframes for In Situ Antibacterial Activity Based on Oxidative and Physical Damages
Authors: Liu Pei , Wu Yuzheng , Mehrjou Babak , Tang Kaiwei , Wang Guomin , Chu Paul K.
Published: March 2022

Gold nanoparticles (GNPs) with oxidase and peroxidase properties are great candidates for antibiotic‐mimicking materials due to reactive oxygen species (ROS) production. However, the bioenzymic properties are not long‐lasting due to the short lifespan of ROS and have only been observed from GNPs with a size of less than 20 nm, thus making the synthesis laborious and inefficient. Herein, GNPs with controllable size and effective ROS utilization are synthesized by an environmentally green process using natural phenols extracted from plants as the reducing and capping reagent. Functional metallic ions are chelated by taking advantage of the coordinating properties of phenols to form the versatile nanoframe (pGNP‐Fe) that can self‐assemble onto bacteria due to the inherent attraction rendered by phenols, and the physical pressure causes bacterial membrane damage. During internalization in bacteria, the cascade process resulting from the enzyme‐like properties generates cytotoxic reactive ROS via oxidization, and the Fenton reaction enhances the antibacterial efficiency. This dual physical/chemical antibacterial process obviates the need for external antibiotics and antibacterial agents, which may otherwise pose toxicity in vivo. The fabrication strategy and materials properties described here provide insights into the design of antibiotic‐mimicking materials based on enzymatic and physical effects.
[LiCl2]− Superhalide: A New Charge Carrier for Graphite Cathode of Dual‐Ion Batteries
Authors: Kim Keun‐il , Tang Longteng , Mirabedini Pegah , Yokoi Amika , Muratli Jesse M. , Guo Qiubo , Lerner Michael M. , Gotoh Kazuma , Greaney Peter Alex , Fang Chong , Ji Xiulei
Published: March 2022

New acceptor‐type graphite intercalation compounds (GICs) offer candidates of cathode materials for dual‐ion batteries (DIBs), where superhalides represent the emerging anion charge carriers for such batteries. Here, the reversible insertion of [LiCl2]− into graphite from an aqueous deep eutectic solvent electrolyte of 20 m LiCl + 20 m choline chloride is reported. [LiCl2]− is the primary anion species in this electrolyte as revealed by the femtosecond stimulated Raman spectroscopy results, particularly through the rarely observed H–O–H bending mode. The insertion of Li–Cl anionic species is suggested by 7Li magic angle spinning nuclear magnetic resonance results that describe a unique chemical environment of Li+ ions with electron donors around. 2H nuclear magnetic resonance results suggest that water molecules are co‐inserted into graphite. Density functional theory calculations reveal that the anionic insertion of hydrated [LiCl2]− takes place at a lower potential, being more favorable. X‐ray diffraction and the Raman results show that the insertion of [LiCl2]− creates turbostratic structure in graphite instead of forming long‐range ordered GICs. The storage of [LiCl2]− in graphite as a cathode for DIBs offers a capacity of 114 mAh g−1 that is stable over 440 cycles.
The Fluorine‐Rich Electrolyte as an Interface Modifier to Stabilize Lithium Metal Battery at Ultra‐Low Temperature
Authors: Zhang Da , Zhu DaWei , Guo WenYao , Deng ChenWei , Xu QunJie , Li HeXing , Min YuLin
Published: March 2022

Lithium (Li) metal batteries (LMBs) are still limited by lithium dendrite growth and solvated structure at low temperatures. A stable solid electrolyte interface (SEI) and solvent sheath structure are the future directions of liquid metal battery development. However, most artificial SEIs and electrolytes cannot meet the original objective of high conductivity and low nucleation potential multifunctional design. To address this challenge, an electrolyte with excellent high current density and low‐temperature performance is reported here. In this electrolyte environment, the thickness and microstructure of the “Chain Link Ships” SEI are formed. Moreover, the additives improve the desolvation ability of Li+ in the ester electrolytes. Under the harsh environment (−30 °C), the average coulombic efficiency (CE) of the Li||copper (Cu) battery reaches 98% after 200 cycles. Even at −40 °C, the Li||LiFePO4 (LFP) battery shows 90% capacity retention after 100 cycles at the cathode‐limited areal capacity (5 mAh cm−2). Furthermore, at 30 °C, the Li||LFP battery can cycle stably for 1200 cycles at 5 C, and the capacity retention reaches 93.5%. This addition strategy provides insights into the commercial application of new solvated structure electrolytes and a new approach for commercial low‐temperature LMBs.
Comment on “Wide‐Range‐Tunable p‐Type Conductivity of Transparent CuI1‐xBrx Alloy”
Authors: Wang Zhi‐Hao , Wei Su‐Huai , Zhang Xie
Published: March 2022

In a recent article, Yamada et al. proposed to utilize CuI‐CuBr alloys (CuI1‐xBrx) as a hole‐density‐tunable p‐type transparent semiconductor. Employing first‐principles calculations, they attributed the acceptor state to Cu vacancies (VCu). Despite the interesting experimental demonstration, it is found that the first‐principles results in the paper are unphysical and misleading due to the adoption of an incorrect level of theory and the lack of a rigorous methodology for computing defect formation energies. Below are the specific concerns.
Hierarchical Therapeutic Ion‐Based Microspheres with Precise Ratio‐Controlled Delivery as Microscaffolds for In Situ Vascularized Bone Regeneration
Authors: Wan Zhuo , Yuan Zuoying , Li Yechen , Zhang Yanling , Wang Yue , Yu Yingjie , Mao Jianping , Cai Qing , Yang Xiaoping
Published: March 2022

Therapeutic ions, such as Si and Mg, play vital roles in regulating metabolism and promoting tissue repair, hence providing an efficient strategy in tissue engineering. The regenerative outcome is strongly dependent on the targeted delivery and controlled release of therapeutic ions. Nevertheless, it remains challenging to deliver multiple ions at controlled manners and ratios. Herein, hierarchical therapeutic ion‐based microspheres are fabricated. The coordinated release of Mg and Si ions at pre‐set ratios is achieved, based on which, Mg favors osteogenesis by inducing highly efficient cell recruitment and angiogenesis, and Si promotes massive collagen secretion and biomineralization to accelerate the bone maturation process. These therapeutic ion‐based microspheres (namely PNM2) can steadily release Mg and Si ions at an optimized ratio of 2:1, which shows the most significant synergistic effect on angiogenesis and osteogenesis. Furthermore, in a rat calvarial defects model, the volume and maturity of the vascularized neo‐bone tissue regenerated with PNM2 microspheres are comparable with or even surpassing those defects regenerated with growth factors and/or cell‐laden scaffolds. Overall, this platform provides a controllable strategy for the coordinated delivery of Mg/Si ions, opening a new avenue for developing therapeutic ion‐based microscaffold for tissue engineering.
Toward the Rational Design of Mid‐Infrared Nonlinear Optical Materials with Targeted Properties via a Multi‐Level Data‐Driven Approach
Authors: Cai Wenbing , Abudurusuli Ailijiang , Xie Congwei , Tikhonov Evgenii , Li Junjie , Pan Shilie , Yang Zhihua
Published: March 2022

Design and exploratory synthesis of new mid‐infrared (mid‐IR) nonlinear optical (NLO) materials are urgently needed for modern laser science and technology because the widely used IR NLO crystals still suffer from their inextricable drawbacks. Herein, a multi‐level data‐driven approach to realize fast and efficient structure prediction for the exploration of promising mid‐IR NLO materials is proposed. Techniques based on machine learning, crystal structure prediction, high‐throughput calculation and screening, database building, and experimental verification are tightly combined for creating pathways from chemical compositions, crystal structures to rational synthesis. Through this data‐driven approach, not only are all known structures successfully predicted but also five thermodynamically stable and 50 metastable new selenides in AIBIIISe2 systems (AI = Li, Na, K, Rb, and Cs; BIII = Al and Ga) are found, among which eight outstanding compounds with wide bandgaps (> 2.70 eV) and large SHG responses (>10 pm V−1) are suggested. Moreover, the predicted compounds I2d‐LiGaSe2 and I4/mcm‐KAlSe2 are successfully obtained experimentally. In particular, LiGaSe2 exhibits a robust SHG response (≈2 × AGS) and long IR absorption edge that can cover two atmospheric windows (3–5, 8–12 µm). Simultaneously, this new research paradigm is also applicative for discovering new materials in other fields.
Dendrites‐Free Lithium Metal Anode Enabled by Synergistic Surface Structural Engineering
Authors: Di Jie , Yang Jin‐Lin , Tian Han , Ren Pengfei , Deng Yirui , Tang Wenhao , Yan Wenqi , Liu Ruiping , Ma Jianmin
Published: March 2022

Lithium (Li) metal with high specific capacity and low redox potential is widely considered as a potential anode for lithium‐ion batteries (LIBs) with high energy density. However, the catastrophic dendrites growth, “dead Li” formation, and surface passivation hinder its practical application. Herein, a selective artificial solid electrolyte interphase (SEI) layer (Li2Sx, x = 1, 2) protection strategy is adopted, where the tip sites passivation and the uniform Li nucleation in grooves are well combined, which enables reversible Li stripping/plating with high storage capacity and robust electrode framework. The grooves derived patterned array Li with selective Li2Sx artificial SEI (LS@A‐Li) exhibit over 1800 h cycling life at 1.0 mA cm–2/1.0 mAh cm–2 and over 600 h even under 5.0 mA cm–2/10.0 mAh cm–2. The application feasibility of such LS@A‐Li is also confirmed by coupling with commercial LiFePO4 and LiNi0.5Co0.2Mn0.3O2 (NCM523) in the full batteries. This work paves way for the large‐scale application of Li metal anode in lithium‐metal batteries with a facile and efficient fabrication process.
DNA‐Based Nanoarchitectures as Eminent Vehicles for Smart Drug Delivery Systems
Authors: Komiyama Makoto , Shigi Narumi , Ariga Katsuhiko
Published: March 2022

In order to cure diseases efficiently with minimal side effects in sophisticated medicine, eminent drugs must be selectively delivered to diseased parts and allow to work only there. However, most of drug delivery systems (DDSs) previously proposed are not yet sufficiently selective and effective. This review covers recent developments of DDS in which DNA nanoarchitectures are employed as drug carriers. From short DNA fragments, a variety of complicated nanomedicines are fabricated to show unprecedentedly smart DDS functions. Encapsulated drugs are released mostly through controlled disassembly of DNA nanoarchitectures. Recent attention has been focusing to the use of appropriate stimuli to regulate each process in the DDS (delivery of drug, its release, and others) for further improved therapy. As intracellular stimuli for the regulation, various endogenous compounds (e.g., mRNA and enzymes), which are specifically abundant in target cells, are employed. Alternatively, physical perturbation (e.g., light irradiation) is provided from outside of tissues to control DDS. By combining multiple strategies in terms of new concepts, enormously smart DDSs are being achieved. Further progresses of these approaches in the future are guaranteed by complete freedom of molecular design in DNA nanoarchitectonics.
Nontrivial Doping Evolution of Electronic Properties in Ising‐Superconducting Alloys
Authors: Wan Wen , Wickramaratne Darshana , Dreher Paul , Harsh Rishav , Mazin Igor I. , Ugeda Miguel M.
Published: March 2022

Transition metal dichalcogenides offer unprecedented versatility to engineer 2D materials with tailored properties to explore novel structural and electronic phase transitions. In this work, the atomic‐scale evolution of the electronic ground state of a monolayer of Nb1−δMoδSe2 across the entire alloy composition range (0 < δ < 1) is investigated using low‐temperature (300 mK) scanning tunneling microscopy and spectroscopy (STM/STS). In particular, the atomic and electronic structure of this 2D alloy throughout the metal to semiconductor transition (monolayer NbSe2 to MoSe2) is studied. The measurements enable extraction of the effective doping of Mo atoms, the bandgap evolution and the band shifts, which are monotonic with δ. Furthermore, it is demonstrated that collective electronic phases (charge density wave and superconductivity) are remarkably robust against disorder and further shown that the superconducting TC changes non‐monotonically with doping. This contrasting behavior in the normal and superconducting state is explained using first‐principles calculations. Mo doping is shown to decrease the density of states at the Fermi level and the magnitude of pair‐breaking spin fluctuations as a function of Mo content. These results paint a detailed picture of the electronic structure evolution in 2D TMD alloys, which is of utmost relevance for future 2D materials design.
Metallaphotoredox‐Enabled Intermolecular Carbobromination of Alkynes with Alkenyl Bromides
Authors: Yu Wei , Jiao Xiaorui , Fan Yanmin , Zhu Shengqing , Chu Lingling
Published: March 2022

A regioselective intermolecular carbohalogenation of alkynes with alkenyl bromides enabled by dual photoredox and nickel catalysis is described. This dual protocol enables an atom‐economic access to a wide array of brominated 1,3‐dienes from simple starting materials. Broad substrate scope and high regioselectivity are observed. The synthetic utility has been demonstrated and preliminary mechanistic studies have been performed to elucidate the reaction pathway.

magnified image
Prevention of Tumor Growth and Dissemination by In Situ Vaccination with Mitochondria‐Targeted Atovaquone
Authors: Huang Mofei , Xiong Donghai , Pan Jing , Zhang Qi , Wang Yian , Myers Charles R. , Johnson Bryon D. , Hardy Micael , Kalyanaraman Balaraman , You Ming
Published: March 2022

Atovaquone, an FDA‐approved drug for malaria, is known to inhibit mitochondrial electron transport. A recently synthesized mitochondria‐targeted atovaquone increased mitochondrial accumulation and antitumor activity in vitro. Using an in situ vaccination approach, local injection of mitochondria‐targeted atovaquone into primary tumors triggered potent T cell immune responses locally and in distant tumor sites. Mitochondria‐targeted atovaquone treatment led to significant reductions of both granulocytic myeloid‐derived suppressor cells and regulatory T cells in the tumor microenvironment. Mitochondria‐targeted atovaquone treatment blocks the expression of genes involved in oxidative phosphorylation and glycolysis in granulocytic‐myeloid‐derived suppressor cells and regulatory T cells, which may lead to death of granulocytic‐myeloid‐derived suppressor cells and regulatory T cells. Mitochondria‐targeted atovaquone inhibits expression of genes for mitochondrial complex components, oxidative phosphorylation, and glycolysis in both granulocytic‐myeloid‐derived suppressor cells and regulatory T cells. The resulting decreases in intratumoral granulocytic‐myeloid‐derived suppressor cells and regulatory T cells could facilitate the observed increase in tumor‐infiltrating CD4+ T cells. Mitochondria‐targeted atovaquone also improves the anti‐tumor activity of PD‐1 blockade immunotherapy. The results implicate granulocytic‐myeloid‐derived suppressor cells and regulatory T cells as novel targets of mitochondria‐targeted atovaquone that facilitate its antitumor efficacy.
Observation of Anomalously Large Magnetoelectric Coupling in the Hexagonal Z‐Type Ferrite Films
Authors: Shin Kwang Woo , Soroka Miroslav , Shahee Aga , Kim Kee Hoon , Buršík Josef , Kužel Radomír , Vronka Marek , Aguirre Myriam Haydee
Published: March 2022

Although the bulk hexaferrites are known to exhibit strong magnetoelectric (ME) effects near room temperature, the same effects are not realized in a thin film form. Herein, the growth of nearly epitaxial Co2Z‐type hexaferrite Ba0.3Sr2.7Co2Fe24O41 (BSCFO) thin films on a SrTiO3 (111) substrate by a chemical solution deposition method is reported. The reciprocal space mapping on the annealed BSCFO films reveals broadening along the qx directions in the (0014) and (0018) peaks, indicating that the oxygen planes belonging to the off‐centered octahedra have randomly distributed out‐of‐plane tilt to indicate significant disorder in the crystallographic orientation. Quantitative investigations reveal that both ME susceptibility and modulated electric polarization (ΔP) by magnetic field up to 370 K in the BSCFO films are always larger than those of the Co2Z‐type single crystal by ≈2–15 times and further increase upon having enhanced qx broadening in the (0014) and (0018) peaks. As the off‐centered octahedral sites can be a primary source of ΔP as predicted by the p–d hybridization mechanism, these results indicate that effective off‐centering could be further enhanced by the orientational disorder. This study identifies the potential of applying the ME hexaferrite films for multifunctional devices.
Microwave Flexible Electronics Directly Transformed from Foundry‐Produced, Multilayered Monolithic Integrated Circuits
Authors: Qin Guoxuan , Jung Yei Hwan , Zhang Huilong , Jiang Ningyue , Ma Pingxi , Stetson Scott , Racanelli Marco , Ma Zhenqiang
Published: March 2022

Monolithic microwave integrated circuits hold a dominant position in telecom applications, especially in mobile devices with capabilities for wireless connectivity, due to high and repeatable performance, compact form factor, and low cost. With flexible electronic technologies forming the foundation for a rapidly growing wearable and implantable device segment, the need for flexible microwave electronics with levels of performance that match those of rigid counterparts has increased to unprecedented levels. Here, the fabrication processes for transforming a rigid form of foundry‐produced, multilayered monolithic microwave integrated circuit into a flexible format for amplification of radio frequency signals in the gigahertz level are described. The strategy involves a complete replacement of all rigid materials in the integrated circuit that do not provide any active electronic functionality with a soft, silicone elastomer to yield an overall structure that is mechanically compliant. Experimental studies indicate that the transformation process leads to a flexible silicon‐germanium‐based heterojunction bipolar transistor with a maximum oscillation frequency of 49 GHz and a 24 GHz amplifier with a small‐signal gain of 13.2 dB. This approach has potential uses across a diverse set of microwave devices and circuits, in a manner that could enable wireless connectivity using entirely flexible electronics.
Advances and Prospects of 2D Graphene‐Based Materials/Hybrids for Lithium Metal–Sulfur Full Battery: From Intrinsic Property to Catalysis Modification
Authors: Zhang Jing , Jia Lujie , Lin Hongzhen , Wang Jian
Published: March 2022

Rechargeable lithium–sulfur (Li–S) full batteries hold practical promise for next‐generation energy storage system owing to low cost and unparalleled theoretical energy density of 2600 W h kg−1. However, wide commercialization is severely hampered by the poor conductivity of S/Li2S, worrisome polysulfide shuttling effect, sluggish multistep reaction kinetics, and uncontrolled lithium dendrite growth. 2D materials show the advantages in suppressing polysulfide shuttling and boosting lithium diffusion kinetics through rational modifications of surface chemistry and nanostructure design, greatly enhancing battery performances. In this review, the recent developments of 2D graphene‐based materials in propelling the conversion/plating kinetics of Li–S full batteries are highlighted from intrinsic conductive property to adsorption and catalysis modifications. Specifically, with the functionalization of the pore morphology and heteroatom/metal atom doping in the pristine/hybrid matrix, the adsorption ability and the lithium diffusion kinetics are significantly enhanced in both cathodic and anodic side, so that the interconversion kinetics of sulfur species are propelled to inhibit polysulfide shuttling and lithium‐ion flux is homogenized to realize uniform deposition without any dendrite growth. Furthermore, challenges and opportunities for future fully development of Li–S batteries based on 2D graphene‐based materials are prospected from interfacial mechanisms at the atomic/molecular level to large‐scale production.
Cantù syndrome: Report of a patient with a novel variant in KCNJ8 and revision of literature
Authors: Apuril Velgara Erika Solansh , Mariani Milena , Torella Annalaura , Musacchia Francesco ,   Telethon Undiagnosed Diseases Program (TUDP) consortium, Nigro Vincenzo , Selicorni Angelo
Published: March 2022

Cantù syndrome (CS) is a rare multisystemic disorder, characterized by congenital hypertrichosis, macrocephaly, facial dysmorphisms, cardiomegaly, vascular, and skeletal anomalies. From the cognitive point of view, most of the patients show a mild speech delay and a few of them present intellectual disability and learning difficulties. To date, most CS‐reported cases are caused by heterozygous ABCC9 gene mutations. Only three patients with CS and heterozygous KCNJ8 gene variants have been reported. The authors here present the fourth case of CS with a variant in KCNJ8 in a 6‐month‐old baby. Diagnosis was reached through Trio‐Whole Exome analysis that revealed a de novo missense variant in KCNJ8.
Challenges, Prospects, and Emerging Applications of Inkjet‐Printed Electronics: A Chemist's Point of View
Authors: Lemarchand Justin , Bridonneau Nathalie , Battaglini Nicolas , Carn Florent , Mattana Giorgio , Piro Benoit , Zrig Samia , Noël Vincent
Published: March 2022

Driven by the development of new functional inks, inkjet‐printed electronics has achieved several milestones upon moving from the integration of simple electronic elements (e.g., temperature and pressure sensors, RFID antennas, etc.) to high‐tech applications (e.g. in optoelectronics, energy storage and harvesting, medical diagnosis). Currently, inkjet printing techniques are limited by spatial resolution higher than several micrometers, which sets a redhibitorythreshold for miniaturization and for many applications that require the controlled organization of constituents at the nanometer scale. In this Review, we present the physico‐chemical concepts and the equipment constraints underpinning the resolution limit of inkjet printing and describe the contributions from molecular, supramolecular, and nanomaterials‐based approaches for their circumvention. Based on these considerations, we propose future trajectories for improving inkjet‐printing resolution that will be driven and supported by breakthroughs coming from chemistry.
Demonstrating and Unraveling a Controlled Nanometer‐Scale Expansion of the Vacancy Defects in Graphene by CO2
Authors: Rezaei Mojtaba , Villalobos Luis Francisco , Hsu Kuang‐Jung , Agrawal Kumar Varoon
Published: March 2022

A controlled manipulation of graphene edges and vacancies is desired for molecular separation, sensing and electronics applications. Unfortunately, available etching methods always lead to vacancy nucleation making it challenging to control etching. Herein, we report CO2‐led controlled etching down to 2–3 Å per minute while completely avoiding vacancy nucleation. This makes CO2 a unique etchant for decoupling pore nucleation and expansion. We show that CO2 expands the steric‐hindrance‐free edges with an activation energy of 2.71 eV, corresponding to the energy barrier for the dissociative chemisorption of CO2. We demonstrate the presence of an additional configurational energy barrier for nanometer‐sized vacancies resulting in a significantly slower rate of expansion. Finally, CO2 etching is applied to map the location of the intrinsic vacancies in the polycrystalline graphene film where we show that the intrinsic vacancy defects manifest mainly as grain boundary defects where intragrain defects from oxidative etching constitute a minor population.
Temperature‐Reliable Low‐Dimensional Perovskites Passivated Black‐Phase CsPbI3 toward Stable and Efficient Photovoltaics
Authors: Tan Shan , Yu Bingcheng , Cui Yuqi , Meng Fanqi , Huang Chunjie , Li Yiming , Chen Zijing , Wu Huijue , Shi Jiangjian , Luo Yanhong , Li Dongmei , Meng Qingbo
Published: March 2022

Low‐dimensional (LD) perovskites can effectively passivate and stabilize 3D perovskites for high‐performance perovskite solar cells (PSCs). Regards CsPbI3‐based PSCs, the influence of high‐temperature annealing on the LD perovskite passivation effect has to be taken into account due to fact the black‐phase CsPbI3 crystallization requires high‐temperature treatment, however, which has been rarely concerned so far. Here, the thermal stability of LD perovskites based on three hydrophobic organic ammonium salts and their passivation effect toward CsPbI3 and the whole device performance, have been investigated. It is found that, phenyltrimethylammonium iodide (PTAI) and its corresponding LD perovskites exhibit excellent thermal stability. Further investigation reveals that PTAI‐based LD perovskites are mainly distributed at grain boundaries, which not only enhances the phase stability of CsPbI3 but also effectively suppresses non‐radiative recombination. As a consequence, the champion PSC device based on CsPbI3 exhibits a record efficiency of 21.0 % with high stability.
Identifying Performance Descriptors in CO2 Hydrogenation over Iron‐Based Catalysts Promoted with Alkali Metals
Authors: Yang Qingxin , Kondratenko Vita A. , Petrov Sergey A. , Doronkin Dmitry E. , Saraçi Erisa , Lund Henrik , Arinchtein Aleks , Kraehnert Ralph , Skrypnik Andrey S. , Matvienko Alexander A. , Kondratenko Evgenii V.
Published: March 2022

Alkali metal promoters have been widely employed for preparation of heterogeneous catalysts used in many industrially important reactions. However, the fundamentals of their effects are usually difficult to access. Herein, we unravel mechanistic and kinetic aspects of the role of alkali metals in CO2 hydrogenation over Fe‐based catalysts through state‐of‐the‐art characterization techniques, spatially resolved steady‐state and transient kinetic analyses. The promoters affect electronic properties of iron in iron carbides. These carbide characteristics determine catalyst ability to activate H2, CO and CO2. The Allen scale electronegativity of alkali metal promoter was successfully correlated with the rates of CO2 hydrogenation to higher hydrocarbons and CH4 as well as with the rate constants of individual steps of CO or CO2 activation. The derived knowledge can be valuable for designing and preparing catalysts applied in other reactions where such promoters are also used.
Low‐Valent Zirconocene‐Mediated Synthesis of Porphyrin(2.1.2.1)s and Its Extension to Synthesis of a Porphyrin(2.1.2.1) Nanobarrel
Authors: Wu Yidan , Zhao Tingting , Rong Jian , Rao Yutao , Zhou Mingbo , Yin Bangshao , Ni Xinlong , Osuka Atsuhiro , Xu Ling , Song Jianxin
Published: March 2022

Rosenthal's‐reagent‐mediated intramolecular cyclometallation of α,α‐dialkynyldipyrrin nickel(II) complex and subsequent acid treatment afforded a 1,3‐butadiene‐embedded porphyrin(2.1.2.1), 6, which served as a reactive diene towards dienophiles such as dimethyl acetylenedicarboxylate (DMAD) and benzyne to give corresponding Diels–Alder adducts. Diels–Alder reaction of 6 and benzdiyne gave adducts 14, 15 a, and 15 b along with a trace amount of porphyrin(2.1.2.1) barrel 13. Stepwise routes using 14 or 15 a/15 b as a substrate allowed for the synthesis of 13 as a single stereoisomer. The nanobarrel structure for 13 was revealed by X‐ray diffraction, where its cavity held two chloroform molecules via C−H⋅⋅⋅π interaction. DFT calculations revealed that the electrostatic attraction was dominant with binding energy of 32.8 kcal mol−1.
Synthesis and antiproliferative study of phosphorescent multimetallic Re(I)/Au(I) complexes containing fused imidazo[4,5‐f]‐1,10‐phenanthroline core
Authors: Luengo Andrés , Marzo Isabel , Fernández‐Moreira Vanesa , Gimeno M. Concepción
Published: March 2022

Five heterobimetallic ReI/AuI and a tri‐metallic ReI/AuI/ReI species following the formulas fac‐[ReCl (CO)3(N^N^CAuR)]0/+ and [(fac‐[ReCl (CO)3(N^N^C)])2Au]+, where R is an iodide (1), phenylacetylene (2), dodecanethiol (3), 2,3,4,6‐tetra‐O‐acetyl‐1‐thio‐β‐D‐glucopyranose (4) and JohnPhos (5) and N^N^C is the fused imidazo[4,5‐f]‐1,10‐phenanthroline heterotopic ligand, were synthesised and fully characterised by a variety of spectroscopic and analytical techniques. The resultant complexes are luminescent in the orange region, revealing classical metal‐to‐ligand charge transfer (3MLCT) ((Re (dπ) → (N^N^C)(π*)) emission in aerated DMSO solution. The red shifted emission observed on going from 3 to 4 suggests that the electronic properties of the gold ancillary ligand are implicated in the emissive properties. Antiproliferative activity in tumour cell lines, lung (A549) and cervix (HeLa) cells revealed that only complex 4 containing a 2,3,4,6‐tetra‐O‐acetyl‐1‐thio‐β‐D‐glucopyranose as gold ancillary ligand possesses certain cytotoxicity in both cell lines.