bluuebunny/crossref_metadata_2025 huggingface dataset:
Does Twitter language reliably predict heart disease? A commentary on Eichstaedt et al. (2015a)
Authors: Brown Nicholas J.L. , Coyne James C.
Published: September 2018

We comment on Eichstaedt et al.’s (2015a) claim to have shown that language patterns among Twitter users, aggregated at the level of US counties, predicted county-level mortality rates from atherosclerotic heart disease (AHD), with “negative” language being associated with higher rates of death from AHD and “positive” language associated with lower rates. First, we examine some of Eichstaedt et al.’s apparent assumptions about the nature of AHD, as well as some issues related to the secondary analysis of online data and to considering counties as communities. Next, using the data files supplied by Eichstaedt et al., we reproduce their regression- and correlation-based models, substituting mortality from an alternative cause of death—namely, suicide—as the outcome variable, and observe that the purported associations between “negative” and “positive” language and mortality are reversed when suicide is used as the outcome variable. We identify numerous other conceptual and methodological limitations that call into question the robustness and generalizability of Eichstaedt et al.’s claims, even when these are based on the results of their ridge regression/machine learning model. We conclude that there is no good evidence that analyzing Twitter data in bulk in this way can add anything useful to our ability to understand geographical variation in AHD mortality rates.
Population genetics of the main population of brown bears in southwest Asia
Authors: Ambarlı Hüseyin , Mengüllüoğlu Deniz , Fickel Jörns , Förster Daniel W.
Published: September 2018

Genetic studies of the Eurasian brown bear (Ursus arctos) have so far focused on populations from Europe and North America, although the largest distribution area of brown bears is in Asia. In this study, we reveal population genetic parameters for the brown bear population inhabiting the Grand Kaçkar Mountains (GKM) in the north east of Turkey, western Lesser Caucasus. Using both hair (N = 147) and tissue samples (N = 7) collected between 2008 and 2014, we found substantial levels of genetic variation (10 microsatellite loci). Bear samples (hair) taken from rubbing trees worked better for genotyping than those from power poles, regardless of the year collected. Genotyping also revealed that bears moved between habitat patches, despite ongoing massive habitat alterations and the creation of large water reservoirs. This population has the potential to serve as a genetic reserve for future reintroductions in the Middle East. Due to the importance of the GKM population for on-going and future conservation actions, the impacts of habitat alterations in the region ought to be minimized; e.g., by establishing green bridges or corridors over reservoirs and major roads to maintain habitat connectivity and gene flow among populations in the Lesser Caucasus.
Maternal immune activation alters brain microRNA expression in mouse offspring
Authors: Sunwoo Jun‐Sang , Jeon Daejong , Lee Soon‐Tae , Moon Jangsup , Yu Jung‐Suk , Park Dong‐Kyu , Bae Ji‐Yeon , Lee Doo Young , Kim Sangwoo , Jung Keun‐Hwa , Park Kyung‐Il , Jung Ki‐Young , Kim Manho , Lee Sang Kun , Chu Kon
Published: September 2018

Objective

Maternal immune activation (MIA) is associated with an increased risk of autism spectrum disorder (ASD) in offspring. Herein, we investigate the altered expression of microRNAs (miRNA), and that of their target genes, in the brains of MIA mouse offspring.

Methods

To generate MIA model mice, pregnant mice were injected with polyriboinosinic:polyribocytidylic acid on embryonic day 12.5. We performed miRNA microarray and mRNA sequencing in order to determine the differential expression of miRNA and mRNA between MIA mice and controls, at 3 weeks of age. We further identified predicted target genes of dysregulated miRNAs, and miRNA‐target interactions, based on the inverse correlation of their expression levels.

Results

Mice prenatally subjected to MIA exhibited behavioral abnormalities typical of ASD, such as a lack of preference for social novelty and reduced prepulse inhibition. We found 29 differentially expressed miRNAs (8 upregulated and 21 downregulated) and 758 differentially expressed mRNAs (542 upregulated and 216 downregulated) in MIA offspring compared to controls. Based on expression levels of the predicted target genes, 18 downregulated miRNAs (340 target genes) and three upregulated miRNAs (60 target genes) were found to be significantly enriched among the differentially expressed genes. miRNA and target gene interactions were most significant between mmu‐miR‐466i‐3p and Hfm1 (ATP‐dependent DNA helicase homolog), and between mmu‐miR‐877‐3p and Aqp6 (aquaporin 6).

Interpretation

Our results provide novel information regarding miRNA expression changes and their putative targets in the early postnatal period of brain development. Further studies will be needed to evaluate potential pathogenic roles of the dysregulated miRNAs.
Event‐triggered fault detection for discrete‐time LPV systems with application to a laboratory tank system
Authors: Golabi Arash , Davoodi Mohammadreza , Meskin Nader , Mohammadpour Javad
Published: September 2018

This paper investigates a new event‐triggered fault detection methodology for discrete‐time dynamic systems characterized by linear parameter‐varying models. An event‐based linear parameter‐varying observer is presented as the fault detection module to generate the residual signal. Moreover, two event‐triggering conditions are proposed to transmit the sensor and scheduling variable data to the fault detection module only when required. A mixed H−/H∞ formulation of the problem is presented to attenuate the effect of disturbances and the control input on the residual signal, and at the same time to maximize the residual signal sensitivity to fault. A set of linear matrix inequality conditions are obtained to find the solution of the proposed problem based on the concept of the input‐to‐state stability. The proposed methodology is experimentally tested and validated on a laboratory two‐tank system.
Biomimetic GelMPC Micropatterns on Titanium and Their Effects on Platelets and Endothelialization
Authors: Ma Wenyong , Yang Ping , Zhao Yuancong , Huang Nan
Published: September 2018

Currently, poly(2‐Methacryloyloxyethyl phosphorylcholine) (PMPC) is widely used for surface modification of biomaterials, but micropatterned immobilization of PMPC on Ti is not so common. To establish micropattern for improving hemocompatibility and orderly endothelialization, gelatin, which has good endothelial cell compatibility, is chosen to crosslink with PMPC. GelMPC is synthesized with gelatin and poly(MPC‐co‐methacrylic acid) (PMMPC) via condensation reaction. GelMPC is immobilized on Ti with micropatterned PDMS stamp. FTIR, SEM, and water contact angle demonstrate that the GelMPC micropattern is fabricated successfully. Platelets on GelMPC micropattern are round and not activated. Endothelial cells and smooth muscle cells cultured on GelMPC micropattern show the cells are aligned in the direction of the pattern, simultaneously the NO release of ECs is upregulated and the number of ECs on GelMPC micropattern increase after 3 days’ culture. However, the number of SMCs on GelMPC micropattern is smaller than that on unmodified (Ti and Ti‐PDA) after 1 day and 3 days’ culture. The authors believe that the method will provide a potential solution for regulation of ECs and SMCs and endothelialization of cardiovascular materials.
Multiphasic Collagen Scaffolds for Engineered Tissue Interfaces
Authors: Lausch Alexander J. , Chong Lester C. , Uludag Hasan , Sone Eli D.
Published: September 2018

Hard–soft tissue interfaces pose unique challenges for regeneration due to architectural, mechanical, and compositional changes between tissues, which are difficult to incorporate into tissue engineering scaffolds. Multiphasic scaffolds are needed to better mimic structural and chemical changes through the incorporation of layers with distinct properties. A particular challenge in the production of multilayered constructs is achieving cohesion between layers. Herein, a novel system is developed, which combines sequential collagen self‐assembly and diffusion gradients in mineralization to produce multiphasic collagen scaffolds that have intrinsic connectivity and porosity between layers, with no need for adhesives or heat treatments. The scaffolds incorporate mineralized layers, wherein the mineralized collagen fibrils have intrafibrillar oriented mineral resembling bone, alongside unmineralized layers. The interface between mineralized and unmineralized layers is sharp and well defined, with nonmineralized fibrils inserting into the mineralized layer to create mechanical interlock and cohesion. Inspired by the complex architecture of the periodontal attachment apparatus (bone–ligament–cementum), it is demonstrated that the model system can be applied to the development of a trilayered collagen scaffold with potential for periodontal regeneration.
Dynamic Electronic Doping for Correlated Oxides by a Triboelectric Nanogenerator
Authors: Chen Yuliang , Zhang Ying , Wang Zhaowu , Zhan Taotao , Wang Yi‐Cheng , Zou Haiyang , Ren Hui , Zhang Guobin , Zou Chongwen , Wang Zhong Lin
Published: September 2018

The metal–insulator transition of vanadium dioxide (VO2) is exceptionally sensitive to charge density and electron orbital occupancy. Thus three‐terminal field‐effect transistors with VO2 channels are widely adopted to control the phase transition by external gating voltage. However, current leakage, electrical breakdown, or interfacial electrochemical reactions may be inevitable if conventional solid dielectrics or ionic‐liquid layers are used, which possibly induce Joule heating or doping in the VO2 layer and make the voltage‐controlled phase transition more complex. Here, a triboelectric nanogenerator (TENG) and a VO2 film are combined for a novel TENG‐VO2 device, which can overcome the abovementioned challenges and achieve electron‐doping‐induced phase modulation. By taking advantage of the TENG structure, electrons can be induced in the VO2 channel and thus adjust the electronic states of the VO2, simultaneously. The modulation degree of the VO2 resistance depends on the temperature, and the major variation occurs when the temperature is in the phase‐transition region. The accumulation of electrons in the VO2 channel also is simulated by finite element analysis, and the electron doping mechanism is verified by theoretical calculations. The results provide a promising approach to develop a novel type of tribotronic transistor and new electronic doping technology.
A Simple and Fast Electrochemical CO2 Sensor Based on Li7La3Zr2O12 for Environmental Monitoring
Authors: Struzik Michal , Garbayo Inigo , Pfenninger Reto , Rupp Jennifer L. M.
Published: September 2018

In the goal of a sustainable energy future, either the energy efficiency of renewable energy sources is increased, day‐to‐day energy consumption by smart electronic feedback loops is managed in a more efficient way, or contribution to atmospheric CO2 is reduced. By defining a next generation of fast‐response electrochemical CO2 sensors and materials, one can contribute to local monitoring of CO2 flows from industrial plants and processes, for energy management and building control or to track climate alterations. Electrochemical Li+‐garnet‐based sensors with Li7La3Zr2O12 solid electrolytes can reach notable 1 min response time at lowered operation temperatures to track 400–4000 ppm levels of CO2 when compared with state‐of‐the‐art NASICON‐based sensors. By using principles of redefining the electrode electrochemistry, it is demonstrated that Li6.75La3Zr1.75Ta0.25O12 can be used to alter its classic use as energy‐storage function to gain additional functions such as CO2 tracking.
A Simple Vacuum‐Based Microfluidic Technique to Establish High‐Throughput Organs‐On‐Chip and 3D Cell Cultures at the Microscale
Authors: Visone Roberta , Ugolini Giovanni Stefano , Vinarsky Vladimir , Penati Miriam , Redaelli Alberto , Forte Giancarlo , Rasponi Marco
Published: September 2018

Microfluidic‐based 3D cell culture and organs‐on‐chip have proved able to generate accurate in vitro models of human physiology. Their widespread application and adoption are however hampered by limited scalability and throughput. Here, a novel strategy is described to significantly enhance the throughput of microfluidic systems for 3D cell culture and organs‐on‐chips. A series of 3D culture chambers (up to 96 replicates) can be seeded with a single pipetting operation and a system of normally closed microfluidic valves ensures the resulting 3D microtissues are independent. Devices fabricated with this design principle are employed to perform 3D cultures of rat cardiac fibroblasts and profile two known drugs (doxorubicin, sotalol) in terms of cytotoxicity. In addition, human contractile cardiac microtissues is generated using iPSC‐derived cardiac myocytes and functional assays on microtissues calcium transients after treatment with a known chronotropic drug (verapamil) are performed. The systems here described thus open up new perspective in the scalability of organs‐on‐chip and pave the way to multireplicate 3D cell cultures in microfluidics.
Formation of Tertiary Alcohol via Chelation‐Assisted Nickel(II)‐Catalyzed Addition of Arylboronic Acids to Unactivated 1‐(Quinolin‐8‐yl)ethan‐1‐one
Authors: Wu Shutao , Guo Weijie , Wang Tao , Xie Qingxiao , Wang Jianhui , Liu Guiyan
Published: September 2018

The synthesis of tertiary alcohol via chelation‐assisted nickel‐catalyzed addition of arylboronic acids to unactivated ketones was reported in this study. A series of substituted arylboronic acids was reacted with 1‐(quinolin‐8‐yl)ethan‐1‐one and its derivatives to provide various substituted 1‐aryl‐1‐(quinolin‐8‐yl)ethan‐1‐ols and relevant compounds in medium to good yields. The N‐directing group is essential for the addition reaction of arylboronic acids to these unactivated ketones. Nickel(II) acetylacetonate (10.0 mol%) in combination with sodium iodide (2 equiv.) and potassium carbonate (0.8 equiv.) was identified as the optimal catalytic system for the current transformations.

magnified image
Asymmetric Phosphine‐Catalyzed [4+1] Annulations of o‐Quinone Methides with MBH Carbonates
Authors: Zhou Tao , Xia Tong , Liu Zhenli , Liu Lu , Zhang Junliang
Published: September 2018

Chiral dihydrobenzofuran units are frequently present in molecules with significant biological and pharmaceutical activities. Herein, we present the first enantioselective formal [4+1] annulation of Morita‐Baylis‐Hillman carbonates with o‐quinone methides (o‐QMs) catalyzed by a newly designed chiral phosphine catalyst. Under the mild and eco‐friendly conditions, a wide range of polysubstituted dihydrobenzofurans were obtained in good yields with excellent enantioselectivities.

magnified image
Topology‐Optimized 3D Photonic Structures with Maximal Omnidirectional Bandgaps
Authors: Meng Fei , Jia Baohua , Huang Xiaodong
Published: September 2018

Three‐dimensional photonic crystals with large omnidirectional bandgaps are critical for diverse device applications, but have been challenging to design due to their structural complexity. A topology optimization algorithm based on the evolutionary topology optimization method to design omnidirectional bandgaps on demand is proposed. Considering an asymmetric simple cubic lattice, large bandgaps between any two neighbor bands are successfully realized and novel 3D photonic structures obtained. The topology‐optimized designs have a uniform bicontinuous character, which originates from the orthogonal distribution of electric fields at the bounds of the bandgaps. The distribution of the dielectric material follows the directions of the wave vectors of the maximum frequencies at the lower bounds. Consequently, the macroscopic effective properties, such as permittivity, exhibit corresponding directionality. The isotropy of effective permittivity indicates the flatness of the lower bound and photonic crystals with large bandgaps tend to have isotropic effective permittivity.
Self‐Assembled Hole Transporting Monolayer for Highly Efficient Perovskite Solar Cells
Authors: Magomedov Artiom , Al‐Ashouri Amran , Kasparavičius Ernestas , Strazdaite Simona , Niaura Gediminas , Jošt Marko , Malinauskas Tadas , Albrecht Steve , Getautis Vytautas
Published: September 2018

The unprecedented emergence of perovskite‐based solar cells (PSCs) has been accompanied by an intensive search of suitable materials for charge‐selective contacts. For the first time a hole‐transporting self‐assembled monolayer (SAM) as the dopant‐free hole‐selective contact in p–i–n PSCs is used and a power conversion efficiency of up to 17.8% with average fill factor close to 80% and undetectable parasitic absorption is demonstrated. SAM formation is achieved by simply immersing the substrate into a solution of a novel molecule V1036 that binds to the indium tin oxide surface due to its phosphonic anchoring group. The SAM and its modifications are further characterized by Fourier‐transform infrared and vibrational sum‐frequency generation spectroscopy. In addition, photoelectron spectroscopy in air is used for measuring the ionization potential of the studied SAMs. This novel approach is also suitable for achieving a conformal coverage of large‐area and/or textured substrates with minimal material consumption and can potentially be extended to serve as a model system for substrate‐based perovskite nucleation and passivation control. Further gains in efficiency can be expected upon SAM optimization by means of molecular and compositional engineering.
Occupational asthma associated with bleached chlorine‐free cellulose dust in a sanitary pad production plant
Authors: Knight David , Lopata Andreas L. , Nieuwenhuizen Natalie , Jeebhay Mohamed F.
Published: September 2018

Background

Cellulose is an insoluble plant polysaccharide produced from soft‐wood pulp. Although chronic respiratory effects associated with high cellulose‐based dust levels have been previously described, occupational asthma has not. A 37 year old machine operator in a sanitary pad production factory presented with new‐onset work‐related asthma symptoms for two years.

Methods

The worker underwent clinical, pulmonological and immunological (skin prick tests, serum specific IgE determinations) evaluation using standardised procedures. The cellulose product was subjected to scanning electron microscopy (SEM) examination. A specific inhalation challenge test performed with the cellulose product ensured that dust concentrations were kept below 5 mg/m3.

Results

The subject was not atopic and did not have elevated IgE to pine wood or xylanase. The cellulose product appeared to be free of protein contaminants on SEM. The Work Effect Index computed on serial PEF recordings was elevated (WEI = 3.8).Specific inhalational challenge with the cellulose product dust revealed a late bronchial response (39% drop in FEV1 at 3 hours post challenge).

Conclusion

This is the first reported case of occupational asthma to a cellulose fibre product. A non‐specific immune reaction or irritant response seems likely. These fibres may therefore not be biologically inert. The occupational exposure limit of 10 mg/m3 generally used for cellulose dust appears to be non‐protective.
Evaluating bone remodeling by measuring Hounsfield units in a rabbit model of rhinosinusitis: is it superior to measuring bone thickness?
Authors: Dong Yi , Zhou Bing , Huang Zhenxiao , Huang Qian , Cui Shunjiu , Li Yunchuan , Fan Erzhong , Li Ying , Wang Xinyan
Published: September 2018

Background

The traditional method of evaluating bone remodeling in chronic rhinosinusitis is to measure bone thickness. The objective of this study was to determine the feasibility of measuring the computed tomography (CT) value in Hounsfield units (HU) as an method and explore whether it is superior to measuring bone thickness.

Methods

The study was a prospective animal trial. Twenty normal rabbits were included in the control group, and 60 rabbit models were inoculated with Staphylococcus aureus to induce rhinosinusitis. The rabbit models were divided into 3 groups according to the time of infection. All animals were euthanized after the CT exam. The samples were scored based on mucus and bone changes. The rabbits were divided into negative and positive groups according to whether bone remodeling was observed. We obtained diagnostic threshold values by measuring the bone thickness and HU of each rabbit's maxillary sinus and compared the values obtained using the 2 methods by calculating the area under the receiver operating characteristic curve (AUC).

Results

The AUC for the measured bone thickness was 0.838, the diagnostic threshold was 1.165 mm. The AUC for the measured HU value was 0.937, the diagnostic threshold was 904.5. The correlation coefficients were r1 = 0.645 for the measured bone thickness and r2 = 0.797 for the HU measurement (r2 > r1; p < 0.01).

Conclusion

Evaluating bone remodeling is feasible by measuring either the bone wall thickness or the CT value. However, using CT to evaluate the sinus bones in rabbits with rhinosinusitis appears to be a more valuable option.
ETFDH Mutations and Flavin Adenine Dinucleotide Homeostasis Disturbance Are Essential for Developing Riboflavin‐Responsive Multiple Acyl–Coenzyme A Dehydrogenation Deficiency
Authors: Xu Jingwen , Li Duoling , Lv Jingwei , Xu Xuebi , Wen Bing , Lin Pengfei , Liu Fuchen , Ji Kunqian , Shan Jingli , Li Honghao , Li Wei , Zhao Yuying , Zhao Dandan , Pok Joo Y. , Yan Chuanzhu
Published: September 2018

Objective

Riboflavin‐responsive multiple acyl–coenzyme A dehydrogenation deficiency (RR‐MADD) is an inherited fatty acid metabolism disorder mainly caused by genetic defects in electron transfer flavoprotein–ubiquinone oxidoreductase (ETF:QO). The variant ETF:QO protein folding deficiency, which can be corrected by therapeutic dosage of riboflavin supplement, has been identified in HEK‐293 cells and is believed to be the molecular mechanism of this disease. To verify this hypothesis in vivo, we generated Etfdh
(h)A84T knockin (KI) mice.

Methods

Tissues from these mice as well as muscle biopsies and fibroblasts from 7 RR‐MADD patients were used to examine the flavin adenine dinucleotide (FAD) concentration and ETF:QO protein amount.

Results

All of the homozygous KI mice (Etfdh
(h)A84T/(h)A84T, KI/KI) were initially normal. After being given a high‐fat and vitamin B2–deficient (HF‐B2D) diet for 5 weeks, they developed weight loss, movement ability defects, lipid storage in muscle and liver, and elevated serum acyl‐carnitine levels, which are clinically and biochemically similar to RR‐MADD patients. Both ETF:QO protein and FAD concentrations were significantly decreased in tissues of HF‐B2D–KI/KI mice and in cultured fibroblasts from RR‐MADD patients. After riboflavin treatment, ETF:QO protein increased in proportion to elevated FAD concentrations, but not related to mRNA levels. These results were further confirmed in cultured fibroblasts from RR‐MADD patients.

Interpretation

For the first time, we successfully developed a RR‐MADD mice model and confirmed that FAD homeostasis disturbances played a crucial role on the pathomechanism of RR‐MADD in this mouse model and culture cells from patients. Supplementation of riboflavin may stabilize variant ETF:QO protein by rebuilding FAD homeostasis. Ann Neurol 2018;84:667–681
Finite‐Time Fault‐Tolerant Control for a Class of Non‐Affine Nonlinear System Using Sliding Mode Disturbance Observer
Authors: Zhang Qiang , Wang Cui , Xu Dezhi
Published: September 2018

This study investigates a finite‐time fault‐tolerant control scheme for a class of non‐affine nonlinear system with actuator faults and unknown disturbances. A global approximation method is applied to non‐affine nonlinear system to convert it into an affine‐like expression with accuracy. An adaptive terminal sliding mode disturbance observer is proposed to estimate unknown compound disturbances in finite time, including external disturbances and system uncertainties, which enhances system robustness. Controllers based on finite‐time Lyapunov theory are designed to force tracking errors to zero in finite time. Simulation results demonstrate the effectiveness of proposed method.
Bioanalytical method development and validation of moxidectin in plasma by LC–MS/MS: Application to in vitro metabolism
Authors: Chhonker Yashpal S. , Sleightholm Richard L. , Murry Daryl J.
Published: September 2018

Moxidectin (MOX) has recently been approved by the US Food and Drug Administration for the treatment of river blindness in select populations. It is also being evaluated as an alternative for the use of ivermectin, widespread resistance to which is becoming a global health issue. Moreover, MOX is becoming increasingly used as a prophylactic antiparasitic in the cattle industry. In this study, we developed and validated an LC–MS/MS method of MOX in human, monkey and mouse plasma. The separation was achieved on an ACE C18 (50 × 3.0 mm, 3 μm) column with isocratic elution using 0.1% acetic acid and methanol–acetonitrile (1:1, v/v) as mobile phase. MOX was quantitated using MS/MS with an electrospray ionization source operating in negative multiple reaction monitoring mode. The multiple reaction monitoring precursor ion → product ion transitions for MOX and abamectin (IS) were m/z 638.40 → 236.30 and m/z 871.50 → 565.35 respectively. The MS/MS response was linear over the concentration range 0.1–1000 ng/mL in plasma with a correlation coefficient (r2) of 0.997 or better. The within‐ and between‐day precision (relative standard deviation, RSD) and accuracy were within the acceptable limits per US Food and Drug Administration guidelines. The method was successfully applied to an in vitro metabolic stability study of MOX.
A general gas‐assisted three‐liquid‐phase extraction method for separation and concentration of puerarin, 3′‐methoxydaidzin, puerarinxyloside, daidzin and daidzein from puerariae extract
Authors: Hu Weilun , Shao Qian , Xi Xingjun , Chu Qiao , Lan Tao , Che Fenfang , Liu Yuanyuan , Lu Yanzhen , Wei Yun
Published: September 2018

In this work, a general and novel separation technique gas‐assisted three‐liquid‐phase extraction was established and applied in separating and concentrating isoflavonoids from the actual sample of puerariae extract by one step. For the gas‐assisted three‐liquid‐phase extraction method, optimal conditions were selected: polyethylene glycol 2000 and ethyl acetate as the flotation solvent, pH 5, (NH4)2SO4 concentration 350 g/L in aqueous phase, N2 flow rate 30 mL/min, flotation time 50 min, and flotation twice. Five isoflavonoids compounds puerarin, 3′‐methoxydaidzin, puerarinxyloside, daidzin and daidzein were separated with recoveries of 82, 84, 80, 88 and 89%, respectively. The separated products were purified by preparative high‐performance liquid chromatography, and the purity of the final products was >96%. The established general gas‐assisted three‐liquid‐phase extraction was used to separate anthraquinones from Cassiae Semen under the optimal conditions, and the recoveries were >75%. The experimental results showed that the established gas‐assisted three‐liquid‐phase extraction method is a general technique for separating active compounds from herb extract.
A case for expanding carrier testing to include actionable X‐linked disorders
Authors: Rope Alan F. , Kauffman Tia L. , Himes Pat , Amendola Laura M. , Punj Sumit , Akkari Yassmine , Potter Amiee , Davis James V. , Schneider Jennifer L. , Reiss Jacob A. , Gilmore Mari J. , McMullen Carmit K. , Nickerson Deborah A. , Richards C. Sue , Jarvik Gail P. , Wilfond Benjamin S. , Goddard Katrina A. B.
Published: September 2018

Key Clinical Message

A research study utilizing whole‐genome sequence analysis for preconception carrier screening provided a genome‐first detection of a severe de novo Factor VIII mutation in a woman with implications for pregnancy management and life‐saving interventions of her newborn son, and a challenge to the existing paradigm regarding carrier testing.
Catalytic Conversion of CO2 to Value‐Added Products under Mild Conditions
Authors: Yu Yulv , Huang Jin , Wang Yuan
Published: September 2018

The catalytic synthesis of multi‐carbon alcohols (MCA, CnH2n+1OH, n≥3) and higher hydrocarbons from CO2 and H2 under low or even ambient temperature are realized for the first time over a prepared bimetallic catalyst composed of nanoparticles of Pt and Ru supported on Fe3O4 (Ru−Pt/Fe3O4). At 40 °C, the selectivity for alcohols, MCA, and higher hydrocarbons reached 77.1 %, 4.5 %, and 19.5 %, respectively, while that for methane was only 3.4 % (carbon based). As revealed by isotope tracer experiments using O18 labeled water, in the hydrogenation of CO2 over Ru−Pt/Fe3O4, MCA could form by catalytic hydrolysis of alkyl, a novel reaction pathway enabling the formation of MCA at low temperature, which is different from the previously reported one based on CO insertion at high temperature. It was discovered that in Ru−Pt/Fe3O4, both Ru and Pt nanoparticles played catalytic roles in the reduction of CO2 to CHx species and the carbon‐carbon coupling reaction to form alkyl, while the catalytic hydrolysis of formed long‐chain alkyl occurred on Pt nanoparticles.
Rational Design of Carbon Nitride Materials by Supramolecular Preorganization of Monomers
Authors: Barrio Jesús , Shalom Menny
Published: September 2018

The control over the chemical and electronic properties of carbon nitride‐based materials is highly challenging due to limitations of the traditionally used solid‐state reaction. Tailoring parameters, such as morphology, surface area, or energy band positions, in this kind of materials is essential for the improvement of the overall performance in a given application, namely photo‐ or electrocatalysis, sensing, or water treatment, amongst others. The supramolecular preorganization of carbon‐nitrogen based monomers via non‐covalent interactions prior to the thermal condensation has made it possible to design graphitic carbon nitride‐like (CN) materials and target specific properties. In this review, we discuss the latest developments in the synthesis of CN and other carbon‐based materials from the supramolecular preorganization of monomers and the consequences on the photocatalytic performance. The monomer sequence, solvent, and reaction conditions which determine the final structure of the supramolecular assembly, and therefore the final CN properties after calcination, are thoroughly discussed.
Biosynthesized Iron Sulfide Nanocluster Enhanced Anodic Current Generation by Sulfate Reducing Bacteria in Microbial Fuel Cells
Authors: Murugan Muralidharan , Miran Waheed , Masuda Takuya , Lee Dae S. , Okamoto Akihiro
Published: September 2018

The anodic oxidation of sulfide metabolically generated from sulfate is considered to be the primary mechanism of sulfate reducing bacteria (SRB) to contribute to the current generation in Microbial Fuel Cells (MFCs). However, the other redox active metabolic by‐product of conductive iron sulfide (FeS) has been seldomly studied in the context of anodic current generation. Here, we demonstrate that the biomineralized FeS increased the anodic current production in Desulfovibrio vulgaris Hildenborough, compared with that mediated by diffusive sulfate. Chronoamperometry on indium tin‐doped oxide electrodes (ITO) poised at +0.4 V (vs SHE) in the presence of lactate and sulfate showed that the presence of ferrous ion caused twice more anodic current than that in the absence of the iron. Linear Sweep Voltammetry (LSV), Scanning Electron Microscopy (SEM) and X‐ray Photoelectron Spectroscopy confirmed that the aggregation formation of cells with FeS and FeS2 particles on the surface of the ITO electrode. These iron sulfur precipitates were more oxidized on the anode surfaces once lactate was depleted as electron source. The presented data suggests that biosynthesized FeS mediates the electron transport from D. vulgaris Hildenborough to the electrode surface. Given microbial capability of FeS biosynthesis is general among SRB, the FeS‐mediated mechanism may dominate anodic current generation of SRB in MFCs.
Beyond Common Metal–Metal Bonds, κ3‐Bis(donor)ferrocenyl→Transition‐Metal Interactions
Authors: Ringenberg Mark R.
Published: September 2018

Ligands with 1,1′‐bis(donor)ferrocene motif are capable of a wide range of binding modes, including the trans chelation mode in which there is a Fe−M interaction (κ3‐D,Fe,D), in the form of a dative Fe→TM bond (TM=transition metal). This Minireview will explore the nature of this Fe–TM interaction thorough select examples as well as how to characterize a Fe→TM dative bond using physical, computational, and spectroscopic techniques.
The enzymatic resolution of 1‐(4‐chlorophenyl)ethylamine by Novozym 435 to prepare a novel triazolopyrimidine herbicide
Authors: Zhang Yinjun , Cheng Feifei , Yan Hongde , Zheng Jianyong , Wang Zhao
Published: September 2018

The kinetic resolution of (R,S)‐1‐(4‐chlorophenyl)ethylamine was accomplished using a commercial lipase from Candida antarctica (Novozym 435). The performance of this lipase was investigated for the enantioselective amidation of (R,S)‐1‐(4‐chlorophenyl)ethylamine, leaving the target product (S)‐1‐(4‐chlorophenyl)ethylamine in its unreacted form. The effects of various types of solvents and an acyl donor, the molar ratio of the substrate to the acyl donor, and the reaction temperature were studied. The optimum reaction conditions were found to result in amidation with methyl 2‐tetrahydrofuroate at 40°C in methyl tert‐butyl ether, with a substrate/acyl donor molar ratio of 1:2.4. The conversion rate of (R,S)‐1‐(4‐chlorophenyl)ethylamine was 52%, with an enantiomeric excess of 99% towards the unreacted substrate in a reaction time of 22 hours. Finally, using optically pure (S)‐1‐(4‐chlorophenyl)ethylamine as the raw material, the chemical synthesis of (S)‐N‐(1‐(4‐chlorphenyl)ethyl)‐2‐(5,7‐dimethyl‐[1,2,4]triazolo[1,5‐a]pyrimidin‐2‐ylthio)acetamide, a novel triazolopyrimidine herbicide, was achieved, and the total yield and purity were 83.5% and 95.3%, respectively.
Enantioseparation of chiral mandelic acid derivatives by supercritical fluid chromatography
Authors: Ding Jiawei , Zhang Ming , Dai Huixue , Lin Chunmian
Published: September 2018

Mandelic acid and its derivatives are important chiral analogs which are widely used in the pharmaceutical synthetic industry. The present study investigated the enantiomeric separation of six mandelic acids (mandelic acid, 2‐chloromandelic acid, 3‐chloromandelic acid, 4‐chloromandelic acid, 4‐bromomandelic acid, 4‐methoxymandelic acid) on the Chiralpak AD‐3 column by supercritical fluid chromatography. The influences of volume fraction of trifluoroacetic acid, type and percentage of modifier, column temperature, and backpressure on the separation efficiency were investigated. And the enantiomer elution order was determined. The results show that, for a given modifier, the retention factor, the separation factor, and the separation resolution decreased gradually with increasing the volume ratio of the modifier. At the same volume ratio of modifier, the retention factor of the mandelic acid and its derivatives increased in the order of methanol, ethanol, and isopropanol, except 3‐chloromandelic acid. The separation factor and the separation resolution decreased with the increase of column temperature (below the temperature limit). The backpressure affected the enantioseparation process: As the backpressure increased, a corresponding decrease in retention factor was observed. Under the same chiral column conditions, the SFC method exhibited faster and more efficient separation with better enantioselectivity than the HPLC method.
Enantioselective toxic effects and digestion of furalaxyl enantiomers in Scenedesmus obliquus
Authors: Cheng Cheng , Ma Rui , Lu Yuele , Liu Chunxiao , Zhang Wenjun , Di Shanshan , Chen Li , Diao Jinling , Zhou Zhiqiang , Hou Yuxia
Published: September 2018

Research on the enantioselective environmental behavior of chiral pesticides has been a hot spot of environmental chemistry recently. In this study, the acute toxicity and digestion of furalaxyl enantiomers were determined on the aquatic algae Scendesmus obliquus. After exposure for 96 hours, the EC50 values for (S)‐furalaxyl and (R)‐furalaxyl were 13.59 and 15.26 mg/L, respectively. In addition, enantioselectivity was observed from the determined chlorophyll contents and antioxidant enzyme (CAT and SOD) activities of algae cells after exposure to furalaxyl enantiomers for 96 hours. The digestion rate of (S)‐furalaxyl and (R)‐furalaxyl were almost the same in S. obliquus. On the basis of these data, the inactive enantiomers (S)‐ furalaxyl is more toxic than the active one on the non‐target species S. obliquus, indicating that such enantiomeric differences should be taken into consideration in the study of pesticide risk assessment.
Unexpected Structure of a Helical N4‐Schiff‐Base Zn(II) Complex and Its Demetallation: Experimental and Theoretical Studies
Authors: Lamine Walid , Boughdiri Salima , Jeanneau Erwan , Sanglar Corinne , Morell Christophe , Christ Lorraine , Chermette Henry
Published: September 2018

A new Zn‐N4‐Schiff base L=((±)‐trans‐N,N’‐Bis(2‐aminobenzylidene)‐1,2‐diaminocyclohexane) complex was synthesized and fully characterized, showing an unexpected self‐assembled double‐stranded helicate structure. The X‐ray crystal analysis of the Zn2L2 complex ((C40H44N8Zn2,CH2Cl2, a=14.2375(3) Å, b=16.7976(4) Å, c=16.1613(4) Å, monoclinic, P21/n, Z=4) shows a centrosymmetrical structure in which zinc atoms are in distorted tetrahedral environments, revealing an M‐ (R, R) left‐handed helicity in its asymmetric unit. However, it was observed that this dinuclear complex is thermodynamically unstable in the presence of small water amounts and undergoes demetallation into free N4‐Schiff base ligand and ZnO nanoparticles. This hydrolysis process was thoroughly identified and monitored through detailed 1H NMR, DOSY NMR analysis. The reaction mechanism of this demetallation event was elucidated by using the DFT method, involving an activation energy smaller than 13 kcal/mol. Besides, a theoretical mechanism of the demetallation process is given for the first time.
High Resolution for Chemical Shifts and Scalar Coupling Constants: The 2D Real‐Time J‐Upscaled PSYCHE‐DIAG
Authors: Tassoti Sebastian , Novak Predrag , Butts Craig P. , Zangger Klaus
Published: September 2018

The facile determination of chemical shift and scalar coupling constants in NMR spectra is often prevented by spectral overlap and limited resolution. Here, we present a high‐resolution NMR experiment for the simultaneous detection of both resonance frequencies and coupling patterns even with small J‐values. A PSYCHE‐decoupled DIAG (Pure Shift Yielded by Chirp Excitation‐ DIAGonal) experiment, which resolves chemical shift in the indirect dimension of a 2D experiment is combined with real‐time J‐upscaling in order to visualize small coupling constants that would otherwise be hidden in the linewidth of a regular proton or DIAG spectrum.
Determination of Thirteen Trace and Toxic Elements in Urine Using Inductively Coupled Mass Spectrometry
Authors: Velez‐Quinones Maria A. , Xu Hanna , Vo Nhu , Gaitens Joanna M. , McDiarmid Melissa A. , Lewin‐Smith Michael R. , Strathmann Frederick G.
Published: September 2018

We developed and validated a method for the assessment of thirteen separate trace and toxic elements using Inductively Coupled Plasma‐Mass Spectrometry (ICP‐MS). Included elements were as follows: aluminum, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, molybdenum, cadmium, tungsten, and lead. The measurements of all elements in urine samples were conducted using ICAP‐Q ICP‐MS in a single method. The performance characteristics of the assay were determined according to clinical laboratory standards. The assay was linear in the concentration range of 1.0 to 1000.0 µg/liter for all elements. The method was precise and accurate with limits of quantitation of 1 µg/liter for chromium, manganese, cobalt, nickel, copper, cadmium, tungsten, and lead; 2 µg/liter for iron and arsenic; 5 µg/liter for aluminum; and 50 µg/liter for zinc. This method has successfully been used for the assessment of all thirteen elements included in urine and has been shown to be effective as a simple, precise, and sensitive analytical technique for biological monitoring of urine samples. © 2018 by John Wiley & Sons, Inc.
Synthesis, Characterization, and Stability of α‐Keggin‐Type Polyoxotungstate‐Coordinated Mono‐Platinum(II) Complex
Authors: Kato Chika Nozaki , Nagatani Shunpei , Mizuno Takayuki
Published: September 2018

The first example of mono‐platinum(II) complex composed of mono‐lacunary α‐Keggin‐type polyoxotungstate is described. The mono‐platinum(II)‐containing polyoxotungstate [(CH3)4N]4H[α‐PW11O39{cis‐PtII(Me2ppz)}]·5H2O (Me2ppz = N,N′‐dimethylpiperazine) (TMA‐1) was synthesized by a 1:1 stoichiometric reaction of mono‐lacunary α‐Keggin polyoxotungstate, [α‐PW11O39]7–, with cis‐PtCl2(Me2ppz) in an aqueous solution, followed by purification from water. The compound TMA‐1 was characterized by elemental analysis, thermogravimetric/differential thermal analysis (TG/DTA), and Fourier transform infrared (FTIR), ultraviolet‐visible (UV/Vis), and solution {1H, 13C, 31P, 195Pt, and 183W} nuclear magnetic resonance (NMR) spectroscopy. The characterization results indicated that a platinum(II) moiety, [cis‐Pt(Me2ppz)]2+, was coordinated to two oxygen atoms in a mono‐vacant site of [PW11O39]7– with asymmetric configuration, resulting in an overall C1 symmetry. The polyoxoanion [α‐PW11O39{cis‐PtII(Me2ppz)}]5– (1) was more stable in dimethylsulfoxide and water than the α‐Keggin‐type polyoxotungstate‐coordinated mono‐platinum(II) complex, [α‐PW11O39{cis‐Pt(NH3)2}]5–, which was also obtained by the reaction of [α‐PW11O39]7– with cis‐diamminedichloroplatinum(II) in an aqueous solution.
Benyzl Alcohol Dehydrogenative Coupling Catalyzed by Defined Mn and Re PNP Pincer Complexes – A Computational Mechanistic Study
Authors: Wei Zhihong , de Aguirre Adiran , Junge Kathrin , Beller Matthias , Jiao Haijun
Published: September 2018

Density functional theory computations have been carried out to investigate the base free acceptor‐less dehydrogenative coupling of benzyl alcohol to benzyl benzoate catalyzed by defined Mn and Re PNP pincer amido M(CO)2(PNP) and amino HM(CO)2(PNHP) complexes [M = Mn, Re; PNP = N{CH2CH2P(isopropyl)2}2]. Benchmark calculations show that B3PW91 have the best and closest agreement with the experiments than DLPNO‐CCSD(T). Within all proposed elementary steps, the non‐innocent outer‐sphere mechanism incorporating the amido complex and the N–H bond is more kinetically favored than the innocent outer‐sphere mechanism without the amido complex as well as the inner‐sphere mechanism via the de‐coordination of one phosphine ligand to create a vacant site for β‐hydride elimination. The dehydrogenation of hemiacetal to ester represents the rate‐determining step. Both Mn and Re‐based catalysts have close free energy barriers and similar catalytic activity. However, the computed apparent barrier is overestimated on the basis of the experimentally determined TOF for the Mn‐based complexes.
Crystal Chemistry, Optical Spectroscopy and Crystal Field Calculations of Co3TeO6 and Solid Solutions Co3–xZnxTeO6
Authors: Reichartzeder Dominik , Wildner Manfred , Weil Matthias , Ivanov Sergey , Stash Adam , Chen Yu‐Sheng
Published: September 2018

Solid solutions Co3–xZnxTeO6 (x = 0–3) were prepared both in polycrystalline and single‐crystalline form using solid state reactions and chemical vapour transport reactions, respectively. Miscibility between the isotypic end members was established over the complete range (C2/c, Z = 12, a ≈ 14.85, b ≈ 8.83, c ≈ 10.34 Å, β ≈ 93°). Crystal structure determinations, performed on basis of single crystal laboratory X‐ray (at 295 K) and synchrotron (at 10 and 100 K) data of Co3TeO6 and selected solid solutions, revealed no structural phase transition and allowed a detailed insight into the Co → Zn substitution mechanism. The coordination polyhedra of the five crystallographically independent M2+ cations are distorted octahedra (for three cations), one distorted tetrahedron and one distorted square pyramid. With increasing Zn content the polyhedral distortions increase, and the preference of the Zn2+ cation for the tetrahedral coordination becomes distinctive. Optical absorption and diffuse reflectance spectroscopy reveal extraordinary strong crystal field absorption effects, over wide x ranges predominantly governed by Co2+ in the single tetrahedral and one strongly acentric distorted octahedral site. Superposition Model crystal field calculations yield intrinsic and power‐law exponent parameters in general agreement with previous data for Co2+. The five cation sites show comparatively high crystal field strengths at generally very low interelectronic repulsion parameters, indicating prominent covalent contribution to Co–O bonding in Co3–xZnxTeO6 solid solutions.
Selective Synthesis and Thermodynamic Relations of Polymorphic Co(NCS)2‐4‐Dimethylaminopyridine Coordination Compounds
Authors: Neumann Tristan , Jess Inke , Pielnhofer Florian , Näther Christian
Published: September 2018

Reaction of Co(NCS)2 with 4‐dimethylaminopyridine (DMAP) leads to the formation of four new compounds. The crystal structures of Co(NCS)2(DMAP)2(H2O)2·2H2O (1), Co(NCS)2(DMAP)2(MeOH)2 (2) and Co(NCS)2(DMAP)2(MeCN)2 (3) consist of discrete simple solvato complexes in which the Co cations are octahedrally coordinated by two terminally N‐bonded thiocyanate anions, two DMAP ligands as well as two solvato ligands. Co(NCS)2(DMAP)2 (4/II) also forms discrete complexes, but the Co cations are tetrahedral coordinated by two anionic ligands and two DMAP ligands. Upon heating, the hydrate 1 transforms into 4/II, whereas the methanol solvate 2 transforms into a new polymorphic modification of Co(NCS)2(DMAP)2 (4/I). For structure determination the corresponding Zn(NCS)2 compound was prepared that is isotypic to 4/I. Solvent mediated conversion experiments prove that 4/II represents the thermodynamic stable form at room‐temperature and density functional theory (DFT) calculations indicate that this form is also stable at 0 K. Upon heating both modifications show melting with the higher melting polymorph 4/I having the lower melting enthalpy. Temperature dependent X‐ray powder diffraction shows that 4/II transforms into 4/I upon heating. All experimental results indicate, that both modifications are related by enantiotropism.
Structural Diversity in Ni Chain Coordination Polymers: Synthesis, Structures, Isomerism and Magnetism
Authors: Jochim Aleksej , Rams Michał , Neumann Tristan , Wellm Carsten , Reinsch Helge , Wójtowicz Gabriela M. , Näther Christian
Published: September 2018

Reaction of Ni(NCS)2 with different co‐ligands based on pyridine derivatives substituted in 4‐position leads to the formation of 1D coordination polymers with the composition [Ni(NCS)2(co‐ligand)2]n, in which the metal cations are coordinated octahedrally by two S‐ and two N‐bonding thiocyanate anions as well as two neutral co‐ligands and are linked into chains by µ‐1,3‐bridging thiocyanate anions. Dependent on the nature of the co‐ligand, novel isomers with linear and corrugated chains are observed, in which the Ni cations are trans‐ or cis‐cis‐trans coordinated. This also includes a dimer and two isomeric chain compounds with 4‐chloropyridine as ligand, of which one is metastable at room‐temperature. For all these compounds, together with several additional Ni(NCS)2 chain compounds, the values of the intrachain exchange interaction J are extracted based on magnetic measurements. The values of J for 13 different Ni(NCS)2 compounds are compared with the structural results to investigate if there are some simple relations between the magnetic exchange, the metal coordination and the chain geometry. The low temperature magnetic properties of the Ni(NCS)2 dimer and the chain compounds are also discussed based on magnetic and specific heat measurements.