bluuebunny/crossref_metadata_2025 huggingface dataset:
An Enantioconvergent and Concise Synthesis of Lasonolide A
Authors: Yang Lin , Lin Zuming , Shao Shunjie , Zhao Qian , Hong Ran
Published: October 2018

Efficient access to medicinally significant natural products is an essential basis for the development of pharmaceuticals. The limited availability of marine natural products impedes broad biological evaluation. Despite several elegant syntheses of (−)‐lasonolide A having been reported, a practical synthesis of this potent anticancer polyketide remains elusive. Based on the application of borane as a traceless protecting group and the development of an unprecedented bissulfone reagent for Julia olefination, (−)‐lasonolide A was assembled in an enantioconvergent manner through the application of stereoselective hydroboration, allylation, and oxidation. This concise route may provide a realistic solution for accessing derivatives and analogues.
Enhancing the Efficacy of Photodynamic Therapy through a Porphyrin/POSS Alternating Copolymer
Authors: Jin Jianqiu , Zhu Yucheng , Zhang Zhenghe , Zhang Weian
Published: October 2018

Aggregation‐induced quenching (AIQ) of photosensitizers greatly reduces the quantum yield of singlet oxygen generation and mitigates the efficacy of photodynamic therapy (PDT). We have prepared an alternating copolymer starting from 4‐vinylbenzyl‐terminated tetraphenylporphyrin (VBTPP) and maleimide isobutyl polyhedral oligomeric silsesquioxane (MIPOSS), via alternating reversible addition–fragmentation chain transfer (RAFT) polymerization. Porphyrin and POSS are installed on the amphiphilic block copolymers backbone in an alternating fashion and POSS completely inhibits the aggregation of porphyrin units via stacking. The amphiphilic block copolymer can self‐assemble into nanoparticles and its application in PDT treatment was tested. These porphyrin‐containing polymeric nanoparticles display high photochemical yield and phototoxicity in vitro and in vivo, providing a novel strategy to enhance the PDT efficacy.
Effects of organomodified muscovite on the properties of acrylonitrile–butadiene–styrene nanocomposites
Authors: Che Ismail Nor Hafizah , Md. Akil Hazizan
Published: October 2018

In this research, we investigated the mechanical and thermal properties of acrylonitrile–butadiene–styrene (ABS)–clay nanocomposites and correlated them with morphological characterizations. We prepared nanocomposites of ABS–clay by melt compounding in a Haake internal mixer. In this study, we investigated the influence of the ion‐exchange process and clay loading on the nanocomposite structure and characterized the nanocomposites with wide‐angle X‐ray diffraction (WAXD), transmission electron microscopy (TEM), contact angle measurement, field emission scanning electron microscopy (FESEM), tensile properties, hardness testing, and thermogravimetric analysis. The ABS–organomuscovite nanocomposites in this study displayed a higher tensile strength than ABS–muscovite. The modified muscovite indicated a 13% modulus elasticity in the ABS nanocomposites, whereas the elongation at break was detrimentally affected compared to that of the neat ABS. The WAXD and TEM results show the presence of mixed intercalated and exfoliated structures. FESEM analysis further revealed a good dispersion and interfacial adhesion of clay layers after subsequent modification. The contact angle measurements showed that the incorporation of organoclay was able to improve the hydrophobicity of the ABS nanocomposites. Finally, the hardness and thermal stability of the nanocomposites improved with the incorporation of modified muscovite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46827.
Activation of Small Molecules by Compounds that Contain Triple Bonds Between Heavier Group‐14 Elements
Authors: Guo Jing‐Dong , Sasamori Takahiro
Published: October 2018

Dimetallynes (RE≡ER; E=Si, Ge, Sn, Pb), i.e., systems that contain triple bonds between heavier group‐14 elements represent the heavier homologues of alkynes. The high reactivity of disilynes, digermynes, distannynes, and diplumbynes can be interpreted in terms of their unique bonding situation, which includes a trans‐bent structure, a small HOMO–LUMO gap, a partial diradical character, their electronic nature, and interactions between bulky substituents. Relatively recent developments in the area of sterically demanding substituents have permitted isolating some stable compounds with a triple bond between heavier group‐14 elements. The structural features of these triple‐bonded compounds and their reactivity toward small molecules have been investigated using experimental and theoretical approaches. This review focuses on recent developments regarding the reactivity of stable compounds with a triple bond between heavier group‐14 elements toward small molecules, where the results were examined using quantum chemical methods. A comprehensive review on carbon chemistry is beyond the scope of this focus review.
Dissolvable Microcarriers Allow Scalable Expansion And Harvesting Of Human Induced Pluripotent Stem Cells Under Xeno‐Free Conditions
Authors: Rodrigues André L. , Rodrigues Carlos A. V. , Gomes Ana R. , Vieira Sara F. , Badenes Sara M. , Diogo Maria M. , Cabral Joaquim M.S.
Published: October 2018

The development of bioprocesses capable of producing large numbers of human induced pluripotent stem cells (hiPSC) in a robust and safe manner is critical for the application of these cells in biotechnological and medical applications. Scalable expansion of hiPSC is often performed using polystyrene microcarriers, which have to be removed from the cell suspension using a separation step that causes loss of viable cells. In this study, application of novel xeno‐free dissolvable microcarriers (DM) for an efficient and integrated expansion and harvesting of hiPSC is demonstrated. After an initial screening under static conditions, hiPSC culture using DM is performed in dynamic culture, using spinner‐flasks. A maximum 4.0 ± 0.8‐fold expansion is achieved after 5 days of culture. These results are validated with a second cell line and the culture is successfully adapted to fully xeno‐free conditions. Afterwards, cell recovery is made within the spinner flask, being obtained a 92 ± 4% harvesting yield, which is significantly higher than the one obtained for the conventional filtration‐based method (45 ± 3%). Importantly, the expanded and harvested hiPSC maintain their pluripotency and multilineage differentiation potential. The results here described represent a significant improvement of the downstream processing after microcarrier‐based hiPSC expansion, leading to a more cost‐effective and efficient bioprocess.
Anatomical Basis of the Intermediate Dorsal Pedal Neurocutaneous Perforator Pedicled Propeller Flap: A Cadaveric Dissection
Authors: Huang Lei , Pafitanis Georgios , Song Dajiang , Hu Deqing , Niu Peng , Hong Xu , Qi Ruilin , Wei Xudong , Zheng Heping
Published: October 2018

Soft tissue defects of the forefoot represent a challenging surgical modality to reconstructive microsurgeons. This study describes the anatomical basis and design of the perforator‐based intermediate dorsal pedal neurocutaneous vascular flap. Thirty fresh human lower limb specimens were injected with red latex and used for dissection of the dorsal vascular and neural anatomy of the foot. The direction and distribution of the intermediate dorsal cutaneous nerve and the vascular anatomy of the third dorsal artery of the plantar arch, along with the intermediate dorsal neurocutaneous nutrient vessels, were mapped. A simulated flap elevation procedure was performed on one fresh cadaver specimen. A clinical series of five cases is presented to demonstrate the feasibility of using the perforator‐based intermediate dorsal pedal neurocutaneous vascular flap to reconstruct soft‐tissue defects of the forefoot. The intermediate dorsal cutaneous nerve usually originates from the lateral branch of the superficial peroneal nerve. Crossing the surface of the cruciate ligament, it descends distally to the proximal part of the fourth intermetatarsal space and divides into the third and fourth dorsal metatarsal branches. The intermediate dorsal cutaneous neural nutrient vessels, which are multi‐segmental and polyphyletic, offer innervation to the skin paddle of the flap elevated on the basis of the third dorsal perforator of the plantar arch. This perforator occupies a relatively constant position in the proximal part of the intermetatarsal space. It sends multiple tiny branches toward the intermediate dorsal cutaneous neural or paraneural nutrient vessel chain. In terms of clinical application, all flaps survived completely; one patient had partial loss of the skin graft. The design and anatomical basis of the intermediate dorsal pedal neurocutaneous vascular flap based on the third dorsal perforator of the plantar arch is a reliable reconstructive option for reconstructing small soft tissue defects in the forefoot. Clin. Anat. 31:1077–1084, 2018. © 2018 Wiley Periodicals, Inc.
Structure and Catalytic Mechanism of a Bacterial Friedel–Crafts Acylase
Authors: Pavkov‐Keller Tea , Schmidt Nina G. , Żądło‐Dobrowolska Anna , Kroutil Wolfgang , Gruber Karl
Published: October 2018

C−C bond‐forming reactions are key transformations for setting up the carbon frameworks of organic compounds. In this context, Friedel–Crafts acylation is commonly used for the synthesis of aryl ketones, which are common motifs in many fine chemicals and natural products. A bacterial multicomponent acyltransferase from Pseudomonas protegens (PpATase) catalyzes such Friedel–Crafts C‐acylation of phenolic substrates in aqueous solution, reaching up to >99 % conversion without the need for CoA‐activated reagents. We determined X‐ray crystal structures of the native and ligand‐bound complexes. This multimeric enzyme consists of three subunits: PhlA, PhlB, and PhlC, arranged in a Phl(A2C2)2B4 composition. The structure of a reaction intermediate obtained from crystals soaked with the natural substrate 1‐(2,4,6‐trihydroxyphenyl)ethanone together with site‐directed mutagenesis studies revealed that only residues from the PhlC subunits are involved in the acyl transfer reaction, with Cys88 very likely playing a significant role during catalysis. These structural and mechanistic insights form the basis of further enzyme engineering efforts directed towards enhancing the substrate scope of this enzyme.
Highly Stretchable and Compressible Self‐Healing P(AA‐co‐AAm)/CoCl2 Hydrogel Electrolyte for Flexible Supercapacitors
Authors: Dai Li‐xin , Zhang Wei , Sun Lu , Wang Xing‐huo , Jiang Wei , Zhu Ze‐wen , Zhang Heng‐bin , Yang Chun‐cai , Tang Jun
Published: October 2018

We report a novel tough self‐healing electrolyte on the basis of poly (acrylic acid‐co‐acrylamide) cross‐linked by divalent cobalt ions (Co2+) (P(AA‐co‐AAm)/CoCl2). Intermolecular and intramolecular hydrogen bonding work together with the metal‐coordination between Co2+ and carboxylic ions to form a hydrogel, which can resist various deformations. The hydrogel electrolyte exhibits excellent mechanical performance (elongation at break >1200 %, compressive stress >600 kPa and compressibility >90 %). The established supercapacitor based on P(AA‐co‐AAm)/CoCl2 can hold its capacitance even after bending, twisting, compressing and self‐healing. Moreover, it retains 90 % capacitance after 5000 cycles. Our electrolyte shows great prospects in manufacture of intelligent flexible equipment.
Elucidation of the Structural Origins and Contrasting Guest–Host Interactions in CO2‐Loaded CdSDB and PbSDB Metal–Organic Frameworks at High Pressures
Authors: Jiang Shan , Hu Yue , Chen Shoushun , Huang Yining , Song Yang
Published: October 2018

PbSDB and CdSDB (SDB=4,4′‐sulfonyldibenzoate) are two structurally related SDB‐based metal–organic frameworks (MOFs) that demonstrate promising potential for selective CO2 adsorption capabilities. The structural stabilities and guest–host interactions between CO2 and PbSDB or CdSDB frameworks at high pressures up to 13 GPa in situ were comparatively investigated by Raman spectroscopy, FTIR spectroscopy, and synchrotron X‐ray diffraction. Although both empty frameworks exhibited high chemical stabilities upon compression, they show different pressure‐induced modifications in crystallinity. This difference can be attributed to their different coordination topologies that result in near isotropic contraction of unit cells for the CdSDB framework but anisotropic for the PbSDB framework. Furthermore, the CO2‐loaded PbSDB and CdSDB frameworks at high pressures show strongly contrasting guest–host interactions in terms of the pressure‐regulated CO2 adsorption sites. In both frameworks, pressure can highly efficiently promote the formation of new CO2 adsorption sites and the enhancement of guest–host interactions. In the CO2‐loaded PbSDB framework, in particular, the peculiar pressure‐tuned CO2 population was observed preferentially on one of the two adsorption sites in response to external compression. These unique guest–host interaction behaviors can also be unambiguously correlated to their different topological origins. These findings for the PbSDB and CdSDB frameworks provide in‐depth understanding of the structure–property relationship, which is of fundamental importance for CO2 storage application in SDB‐based MOFs.
Chiral separation and modeling of quinolones on teicoplanin macrocyclic glycopeptide antibiotics CSP
Authors: Ali Imran , Suhail Mohd , Asnin Leonid
Published: October 2018

New chiral high‐performance liquid chromatography (HPLC) method for the enantiomeric resolution of quinolones is developed and described. The column used was Chirobiotic T (150 × 4.6 mm, 5.0 μm). Three mobile phases used were MeOH:ACN:Water:TEA (70:10:20:0.1%), (60:30:10:0.1%), and (50:30:20:0.1%). The flow rate of the mobile phases was 1.0 mL/min with UV detection at different wavelengths. The values of retention, resolution, and separation factors ranged from 1.5 to 6.0, 1.80 to 2.25, and 2.86 to 6.0, respectively. The limit of detection and quantification ranged from 4.0 to 12 ng and 40 to 52 ng, respectively. The modeling studies indicated strong interactions of R‐enantiomers with teicoplanin chiral selector than S‐enantiomers. The supra molecular mechanism of the chiral recognition was established by modeling and chromatographic studies. It was observed that hydrogen bondings and π‐π interactions are the major forces for chiral separation. The present chiral HPLC method may be used for enantiomeric resolution of quinolones in any matrices.
Relationship between high‐sensitivity C‐reactive protein and subclinical carotid atherosclerosis stratified by glucose metabolic status in Chinese adults
Authors: Su Haiyan , Pei Yinghua , Tian Chunling , Zhang Qing , Liu Li , Meng Ge , Yao Zhanxin , Wu Hongmei , Xia Yang , Bao Xue , Gu Yeqing , Sun Shaomei , Wang Xing , Zhou Ming , Jia Qiyu , Song Kun , Sun Zhong , Niu Kaijun
Published: October 2018

Background

Atherosclerosis is an inflammatory disease. Many studies demonstrated that hyperglycemia is not only increased inflammatory response, but also is a cause of atherosclerosis, implying that glucose metabolic status may be an important stratification factor when analyzing the relationship between inflammatory levels and subclinical carotid atherosclerosis. The aim of the present study is to assess the relationship between inflammatory levels and subclinical carotid atherosclerosis, stratified by different glucose metabolic status in a general population.

Methods

An assessment was performed in 7975 participants living in Tianjin, China. In the present study, we examined subclinical carotid atherosclerosis, as defined by increased carotid intima‐media thickness [IMT] and plaques. Measurements were performed using a carotid artery B‐mode ultrasound system. The glucose metabolic status was defined by the criteria of the American Diabetes Association, and high‐sensitivity C‐reactive protein (hs‐CRP) as an inflammatory indicator, was measured by immunoturbidimetric assay. Multiple logistic models were used to assess a stratified relationship between hs‐CRP levels and subclinical carotid atherosclerosis. Strata were defined according to glucose metabolic status.

Results

The prevalence of increased IMT and plaques were 27.3% and 21.3%, respectively. The adjusted odds ratios (95% confidence interval) for IMT across hs‐CRP quartiles were as follows: 1.00 (reference), 1.10(0.88‐1.38), 1.08(0.86‐1.35) and 1.32(1.06‐1.66) in blood glucose‐normal subjects; 1.00 (reference), 1.33(0.92‐1.91), 1.33(0.93‐1.91), and 1.59(1.10‐2.30) in prediabetic subjects; 1.00 (reference), 0.94(0.54‐1.62), 1.17(0.65‐2.12) and 0.98(0.55‐1.76) in diabetic subjects, respectively. Similar results were observed for plaques.

Conclusions

Our results suggest that inflammatory levels are differently related to subclinical carotid atherosclerosis by the different glucose metabolic status.
Influence of unplanned excisions on the outcomes of patients with stage III extremity soft‐tissue sarcoma
Authors: Traub Frank , Griffin Anthony M. , Wunder Jay S. , Ferguson Peter C.
Published: October 2018

BACKGROUND

Soft‐tissue sarcomas (STSs) are a heterogeneous group of malignant tumors that can be difficult to treat. This is particularly true after incomplete or unplanned excisions and especially for patients with American Joint Committee on Cancer stage III tumors, who are at high risk for relapse. Numerous studies have shown that an inadequate sarcoma excision is associated with a worse prognosis. However, other reports have suggested an improved prognosis for patients with an initial unplanned excision and subsequent re‐excision in comparison with patients who undergo planned primary surgery. The purpose of this study was to determine the impact of an unplanned excision on treatment and subsequent oncologic and functional outcomes for patients with stage III extremity STS.

METHODS

From the prospectively collected database at a tertiary‐referral sarcoma center, all patients with stage III STS of the extremities treated between 1989 and 2010 were identified. Patient records were reviewed to identify patient demographics, tumor details, treatments, complications, and functional and oncologic outcomes.

RESULTS

Five hundred patients with stage III STSs of the extremities were identified, and 94 of these patients (18.8%) were referred after inadequate excisions had been performed elsewhere. All 94 patients with unplanned excisions underwent re‐excision in an attempt to achieve clear margins, and 83% of these patients had residual tumor in the re‐excision specimen. In the re‐excision group, the rates of plastic reconstruction (eg, skin grafts and rotational or free flaps) and amputation were significantly higher in comparison with the rates for patients who underwent a primary planned resection (P = .023 and P = .03, respectively). The rates of local recurrence, metastasis‐free survival, and overall survival were not significantly different between the 2 groups, nor were the functional outcomes.

CONCLUSIONS

Unplanned excision of stage III STS leads to an unfavorable clinical course and necessitates more extensive surgery. As a result of aggressive re‐excision and multidisciplinary treatment, a negative effect on oncologic outcomes cannot be confirmed.
Sentiment classification of micro‐blog comments based on Randomforest algorithm
Authors: Liu Xiao‐Qin , Wu Qiu‐Lin , Pan Wen‐Tsao
Published: October 2018

Sentiment classification of Micro‐blog comments aims to distinguish consumers' attitudes toward a certain brand or an event. A great number of research studies related to sentiment analysis have been conducted based on machine learning methods, such as Support Vector Machine and Naive Bayes, to build the classifier, and some other research studies tried to build one based on emotional thesaurus. However, the rate of accuracy is yet to improve. In order to improve the accuracy rate further, this thesis bases on the Randomforest algorithm to construct an emotional tendency classifier to help the mobile phone service providers to further understand consumers' attitudes toward their brand. The Randomforest algorithm is a bagging algorithm of the ensemble learning with some weak classifiers, which works very well in anti‐noise and reducing the overfitting problem. Finally, a classifier with an 83% accuracy rate for sentiment classification of mobile phone brands on Micro‐blog comments was built based on Randomforest by using R language software.
Study on the posts and performance evaluation model of inpatients in public hospitals based on .NET platform DRGs payment mode
Authors: Lin Xia , Huang Qingjia , Bai Fei , Jin Dun , Lu Wei , Tao Hongbing
Published: October 2018

Performance appraisal is a daily, homework, fair, and open appraisal of each hospital, which can mobilize the enthusiasm and creativity of the employees to the greatest extent so that both the company and the employees can achieve development. At present, the ascendant information revolution has become an important factor in promoting the development of the times. The use of advanced information technology to develop advanced information systems to conduct fair and open assessments of the ever‐increasing number of company employees has become the trend of the times. This article makes a historical review of the development and function of the performance appraisal system, and fully analyzes the new features and new functions of the performance appraisal system in the new period, and details the solution. This system develops and uses .NET development platform and SQL Server 2005 database. Using a distributed approach, the system's development costs have reduced, and the system's maintainability and scalability are improved. This paper studies the establishment of a performance‐based distribution model based on diagnostic relevance grouping theory (DRGs) in public hospitals. Based on the DRGs as a theoretical basis, after a long period of historical data collection, a theoretical model was established, repeated regression calculations, and focused evaluations. A performance‐distribution scheme centered on workload has established to reflect the factors such as the labor risk, technical difficulty, and labor cost of the attending doctors in relation to different patient conditions. The formulation and implementation of the new performance plan embodies the input of labor value and conforms to the spirit of the new medical reform.
Research on the clustering algorithm of the bicycle stations based on OPTICS
Authors: Liu Liangxu , Hu Zhenghua , Zhou Chaolan , Xu Guohu
Published: October 2018

With the development of the sharing traffic economy, the urban fixed‐station parking public bicycle system greatly facilitates the residents to travel. However, the tidal problem has greatly reduced the social utility of the public bicycle system. A step‐by‐step scheduling strategy has been put forward to solve the problem, which firstly clusters the stations according to station locations or the number of bicycles circulating in a station and then perform regional scheduling in each cluster. However, because the clusters obtained by this method do not have the characteristics of a closed small‐world network, the strategy does not cover all stations that require bicycle scheduling. To fix the gap, a station clustering algorithm is proposed, which employs SimRank to calculate the similarity between the stations according to the loan‐to‐return relationship and then adopts the density clustering algorithm of OPTICS (ordering points to identify the clustering structure) to cluster all stations based on the similarity. The data of public bicycle system in Ningbo City, Zhejiang Province of China, is employed to validate the algorithm. The experiment found that the station clustering results have distinct regional characteristics, and the algorithm is competent to divide the scheduling area of public bicycles.
Fluorination‐Induced Evolution of Columnar Packing in Fluorous Triphenylenes and Benzotriphenylenes
Authors: Rippy Kerry C. , DeWeerd Nicholas J. , Kuvychko Igor V. , Chen Yu‐Sheng , Strauss Steven H. , Boltalina Olga V.
Published: October 2018

Use of D3h‐symmetrical triphenylene (TRPH) as a substrate for high‐temperature radical reactions with C4F8I2 under varying conditions resulted in the introduction of four types of fluorinated substituents: ω‐C4F8H, c‐C4F8, c‐C4F4, and c‐C4HF3. In contrast to the previous work on direct (poly)substitutions with RF groups in polycyclic aromatic hydrocarbons (PAHs), in this work regiospecificity, selectivity, and high yield were achieved for TRPH(C4F8) and TRPH(C4F8)3. New single‐crystal structural data for seven compounds combined with literature crystallographic data allowed for the first detailed and precise analysis of the effects of fluorous substituent types, their number, and their position(s) on the TRPH core on the solid‐state packing, and more specifically, the degree of π–π overlap between neighboring molecules, which is linked to charge transport properties. Comparison of isostructural partially fluorinated benzotriphenylenes, 2,3‐TRPH(C4F4) and 2,3‐TRPH(C4HF3), revealed an unexpectedly large (30 %) drop of π–π overlap, when only one fluorine atom was replaced with the hydrogen atom in a C4F4 moiety. Theoretical and potentially practical implications of this work may include further testing and elaboration of computational methods describing solid‐state interactions and predictions of transport properties of organic semiconductors, and further advances in the molecular design of high‐performing TRPH‐based organic materials and supramolecular architectures for organic optoelectronics.
Site‐Selective Cu‐Catalyzed Alkylation of α‐Amino Acids and Peptides toward the Assembly of Quaternary Centers
Authors: San Segundo Marcos , Correa Arkaitz
Published: October 2018

The CuI‐catalyzed selective α‐alkylation of α‐amino acid and peptide derivatives with 2‐alkyl‐1,3‐dioxolanes is reported. This oxidative coupling is distinguished by its site‐specificity, high diastereoselectivity, and chirality preservation and exhibits absolute chemoselectivity for N‐aryl glycine motifs over other amino acid units. Collectively, the method allows for the assembly of challenging quaternary centers, as well as compounds derived from natural products of high structural complexity, which may provide ample opportunities for late‐stage functionalization of peptides.
Network service chains deployment across multiple SDN domains
Authors: Zhang Chuangchuang , Wang Xingwei , Li Fuliang , Huang Min , He Qiang
Published: October 2018

The integration of software‐defined networking (SDN) and network function virtualization (NFV) enables the flexible deployment of network services and significant reduction in service provisioning cost. In particular, SDN, as a new networking paradigm, supports the flexible provisioning of new network services. Meanwhile, in NFV, the service request from end user can be represented as the service function chain (SFC). However, with the continuously increasing of network users and constant enlargement in network scale, the deployment of network services in the large‐scale SDN network, which is composed of multiple SDN domains, becomes more challenging since these SDN domains are managed and maintained by different network operators and service providers. To address the above challenge, in this paper, we study the problem of how to deploy network services across multiple SDN domains optimally. Specifically, we first formulate this problem as an optimization problem by jointly minimizing the total number of SDN domains occupied by SFCs and the corresponding network resource consumption cost. We propose a novel heuristic deployment algorithm to solve this optimization problem. The simulation results demonstrate that the proposed heuristic deployment algorithm is effective and outperforms the comparison algorithms in terms of the total service cost.
During acute graft versus host disease CD28 deletion in donor CD8+, but not CD4+, T cells maintain antileukemia responses in mice
Authors: Uri Anna , Lühder Fred , Kerkau Thomas , Beyersdorf Niklas
Published: October 2018

Donor lymphocyte infusions together with allogeneic hematopoietic stem cell transplantation are routinely used as second‐line treatment for hematological malignancies. Mature T cells in the graft crucially mediate a graft versus leukemia (GvL) response, but also attack healthy tissues in the recipient leading to potentially life‐threatening acute graft versus host disease. Using inducible CD28 knockout C57BL/6 mice as T‐cell donors, we have now assessed whether CD28 costimulation of donor CD4+ and/ or CD8+ T cells is required for an efficient GvL effect after allogeneic T‐cell transplantation into BALB/c recipients. Our results show that CD28 costimulation of donor CD8+ cytotoxic, but not CD4+ helper, T cells was dispensable for curing mice from the BCL‐1 lymphoma. Therefore, donor lymphocyte infusion treated lymphoma‐bearing BALB/c recipient mice showed enhanced long‐term survival when receiving CD28‐deficient as compared to wild‐type donor CD8+ T cells together with wild‐type conventional and regulatory CD4+ T cells. The same was observed when donor CD8+ and conventional and regulatory CD4+ T cells were CD28 deficient. Our data, thus, suggest that systemic CD28 blockade, for example, with the drug FR104 might also reduce acute graft versus host disease in patients after allogeneic hematopoietic stem cell transplantation, while maintaining the protective GvL response.
Efficient Synthesis of Malonate Functionalized Chiral Phosphapalladacycles and their Catalytic Evaluation in Asymmetric Hydrophosphination of Chalcone
Authors: Li Xi‐Rui , Chen Yu , Pang Benjamin Piaoxiang , Tan Jaeyu , Li Yongxin , Pullarkat Sumod A. , Leung Pak‐Hing
Published: October 2018

Four chiral phosphapalladacycle complexes functionalized with the malonate moiety at the chiral carbon have been synthesized via a consecutive asymmetric hydrophosphination and cyclometallation protocol. High conversions were achieved in the P–H addition reaction, which was itself catalyzed by a phosphapalladacycle. Moderate to good enantioselectivities, were obtained for this step depending on the nature of the functional groups present on the naphthalene backbone. In contrast, the outcome of the subsequent cyclometallation reaction relies highly on the character of the functional groups. The catalytic potential of the synthesized phosphapalladacycle complexes was evaluated in the hydrophosphination reaction of chalcone with moderate results.
Photogeneration of Manganese(III) from Luminescent Manganese(II) Complexes with Thiacalixarene Ligands: Synthesis, Structures and Photophysical Properties
Authors: O'Toole Niall , Lecourt Constance , Suffren Yan , Hauser Andreas , Khrouz Lhoussain , Jeanneau Erwann , Brioude Arnaud , Luneau Dominique , Desroches Cédric
Published: October 2018

The photophysical properties of the compound [(ThiaSO2)(MnII)2(DMF)4(H2O)2] (2), ThiaSO2 = p‐tert‐butylsulfonylcalix[4]arene, are presented and compared to the ones of [(ThiaSO2)2(MnII)4F]K (1). The orange luminescence of 2 is attributed, as for 1, to the MnII centred 4T1→6A1 transition and shows, for this type of complex, the weak influence of the Mn2+ coordination and ThiaSO2 conformation on this luminescence, the temperature and pressure dependence and quenching by molecular dioxygen of which are reported for 2. The latter is attributed to energy transfer from the 4T1 state exciting dioxygen to its 1Σ+g state and is responsible for the photosynthesis of the [(ThiaSO2)(MnIII)(DMF)2]Na (3) complex in DMF solution from 1 or 2. This reaction was studied by UV/Visible and EPR spectroscopy. The molecular structure and EPR spectroscopy of 3 are also presented.
DBU‐Promoted Intramolecular Crossed Aldol Reaction: A Facile Access to Indane‐Fused Pyrrolidine
Authors: Yang Heng , Liu Dandan , Yu Qinqin , Xia Siyu , Yu Dan , Zhang Mao , Sun Bing , Zhang Fang‐Lin
Published: October 2018

A new strategy for the facile synthesis of indane‐fused pyrrolidines through DBU‐promoted intramolecular crossed aldol reaction has been developed. The efficiency, compatibility and practicality of this method were demonstrated by a broad substrate scope, mild reaction conditions and gram‐scale synthesis. The further derivatizations of the synthesized diastereoisomers 2a and 2a′ were performed for arylation, alkenylation, amination and etherification, showing high diastereoselectivities. Deuterium labeling experiment suggests a possible carbocation process which leads to the high diastereoselectivity during the transformations of 2a and 2a′. Based on this strategy, the 5‐HT2C agonist V and the antihypertensive agent VI were successfully synthesized through a three‐step synthetic pathway. This new strategy potentially enables a wide exploration of these indane‐fused derivatives applied for pharmaceuticals and related fields.
Trajectories of posttraumatic stress symptoms after whiplash: A prospective cohort study
Authors: Ravn Sophie L. , Karstoft Karen‐Inge , Sterling Michele , Andersen Tonny E.
Published: October 2018

Background

Posttraumatic stress disorder (PTSD) symptoms are highly prevalent after whiplash and associated with pain‐related symptoms. While mutual maintenance between pain and PTSD has been suggested, knowledge on individual differences in the course of these symptoms is needed. The present study aimed to identify trajectories of PTSD symptoms following whiplash and test predictors and functional outcomes of such trajectories.

Methods

In a prospective cohort design with assessments at baseline (<4 weeks), 3 months, and 6 months post‐injury (n = 229, whiplash grade I‐III), we identified PTSD‐trajectories using Latent Growth Mixture Modeling. Predictors (pain, fear‐avoidance‐beliefs, pain‐catastrophizing, depression, age, and gender) were tested using multinomial logistic regression, and group mean differences in physical and psychosocial pain‐related disability at 6 months were tested as outcomes after controlling for baseline levels.

Results

Three trajectories were identified: “Resilient” (75.1%) with little or no PTSD symptoms over time, “Recovering” (10.0%) with high initial PTSD symptom levels, then decreasing substantially, and “Chronic” (14.9%) with high initial PTSD symptom levels and a small increase over time. Initial higher pain and depression levels predicted the recovering and chronic trajectories, while the latter had more pain‐related disability at 6 months compared to both other trajectories.

Conclusions

Three trajectories were identified, with the chronic trajectory suggesting that a significant subset of people does not recover from PTSD symptoms. This class also reported more pain‐related disability. Pain and depression predicted membership, but did, however, not succeed in differentiating between the two high‐starting trajectories, suggesting that targeting PTSD symptoms may be important to ensure recovery.

Significance

Distinct recovery patterns after whiplash were identified with a significant subgroup reporting elevated and slightly increasing PTSD symptoms over time, highlighting both recovery variability and the presence of PTSD symptoms in a significant subgroup of individuals with whiplash. This subgroup also displayed enhanced pain‐related disability over time compared to the recovering and resilient subgroups, thereby linking PTSD symptoms to functional pain outcomes over time. These findings suggest that clinicians should be attentive of potential PTSD symptoms in whiplash patients.
Electrochemical Study on Quantitative Structure‐activity Relationship (QSAR) Analysis under Steady‐state Conditions
Authors: Takaishi M. , Shirai O. , Kitazumi Y. , Kano K.
Published: October 2018

The influence of the volume ratio of the aqueous to 1‐octanol phase on drug delivery under steady‐state conditions in a tubular electrolytic cell composed of an organic phase and two aqueous phases was elucidated. Electrochemical measurements on the transport of six quaternary ammonium chlorides were performed using three types of membrane filters of different thickness. The electric resistance of each system was evaluated, and the distribution coefficient of each chloride was estimated from the extraction experiments. The permeation process within the organic phase was the rate‐determining step for tetrapropylammonium, tetrabutylammonium, tetrapentylammonium and tetrahexylammonium chlorides. On the other hand, for tetraoctylammonium chloride, which was the most hydrophobic ion among the six tested, the salt was easily distributed into the organic phase. Therefore, the rate‐determining step changed to the permeation process within the aqueous phase. In addition, the influence of ion‐pair formation on drug delivery was evaluated.
Evaporative characteristics of sessile nanofluid droplet on micro‐structured heated surface
Authors: Zhu Gui‐Ping , Ong Kian‐Soo , Chong Karen Siew‐Ling , Yao Jia‐Feng , Huang Hu‐Lin , Duan Fei
Published: October 2018

Micro‐structure patterned substrates attract our attention due to the special and programmable wettabilities. The interaction between the liquid and micro/nano structures gives rise to controllable spreading and thus evaporation. For exploration of the application versatility, the introduction of nanoparticles in liquid droplet results in interaction among particles, liquid and microstructures. In addition, temperature of the substrates strongly affects the spreading of the contact line and the evaporative property. The evaporation of sessile droplets of nanofluids on a micro‐grooved solid surface is investigated in terms of liquid and surface properties. The patterned nickel surface used in the experiments is designed and fabricated with circular and rectangular shaped pillars whose size ratios between interval and pillars is fixed at 5. The behavior is firstly compared between nanofluid and pure liquid on substrates at room temperature. For pure water droplet, the drying time is relatively longer due to the receding of contact line which slows down the liquid evaporation. Higher concentrations of nanoparticles tend to increase the total evaporation time. With varying concentrations of graphite at nano scale from 0.02% to 0.18% with an interval at 0.04% in water droplets and the heating temperature from 22 to 85°C, the wetting and evaporation of the sessile droplets are systematically studied with discussion on the impact parameters and the resulted liquid dynamics as well as the stain. The interaction among the phases together with the heating strongly affects the internal circulation inside the droplet, the evaporative rate and the pattern of particles deposition.
Proposal of design rules for ductile X‐CBFS in the framework of EUROCODE 8
Authors: Costanzo Silvia , D'Aniello Mario , Landolfo Raffaele
Published: October 2018

Cross concentrically braced frames (X‐CBFs) are commonly used as primary seismic resisting system, owing to their large lateral stiffness, simplicity of design, and relatively low constructional cost. Current EN 1998‐1 provides design rules theoretically aiming at developing ductile global plastic mechanism, namely enforcing plastic deformations in the diagonal members, while the remaining structural members and connections should elastically behave. However, as widely demonstrated by many existing studies, the design and the corresponding seismic performance of EC8‐compliant X‐CBFs are generally affected by several criticisms, eg, difficulties in sizing of diagonal members, massive and non‐economical structures, and poor seismic behavior. In light of these considerations, the research activity presented in this paper is addressed to revise the design rules and requirements given EN 1998‐1 for X‐CBFs to simplify the design process and to improve the ductility and the dissipative capacity of this structural system. Hence, design rules are proposed for the next version of EN 1998‐1 and numerically validated by means of nonlinear dynamic analyses.
Severity of somatic symptoms in outpatients with anorexia and bulimia nervosa
Authors: Weigel Angelika , Löwe Bernd , Kohlmann Sebastian
Published: October 2018

Objective

Prior studies investigated objective somatic consequences of eating disorders whereas research on subjective somatic symptom severity, that is, profiles of subjective burden of somatic symptoms in patients with anorexia (AN) and bulimia nervosa (BN), is sparse.

Methods

Somatic symptom severity (Patient Health Questionnaire‐15) was investigated in a cross‐sectional consecutive sample of outpatients with AN or BN. Using regression and mediation analyses, effects of somatic symptom severity on days of sick leave during the last 2 weeks and quality of life were examined.

Results

Compared with AN‐outpatients (n = 90, MBMI = 17.2, Mage = 27.9 years, 95% female), BN‐outpatients (n = 63, MBMI = 21.8, Mage = 29.0 years, 93% female) reported a significantly higher somatic symptom severity (p = 0.016). Increased somatic symptom severity predicted days of sick leave during the last 2 weeks (p = 0.036) and physical quality of life (p = <0.001). However, after controlling for depression and anxiety as mediators, somatic symptom severity did no longer predict psychological quality of life (p = n.s.).

Conclusions

Somatic symptom severity is high in both eating disorders. As it is associated with increased sick leave during the last 2 weeks and decreased quality of life, it adds to the psychological burden of AN and BN. Future research should investigate predictors of subjective somatic symptom severity and whether direct somatic symptom management enhances treatment of AN and BN.
Food addiction in Russian adolescents: Associations with age, sex, weight, and depression
Authors: Borisenkov Mikhail F. , Tserne Tatyana A. , Bakutova Larisa A.
Published: October 2018

Objective

Eating disorders are a cause of the recent obesity epidemic. Food addiction (FA) and factors associated with eating disorders have not been adequately studied in adolescents.

Method

The final study sample included 1,144 students. Study participants were asked to indicate their age, sex, and month of birth and fill out the Yale Food Addiction Scale for Children and Zung Self‐Rating Depression Scale.

Results

Of the total number of adolescents studied, 4.5% had FA. It was found that an increased rate of FA diagnosis existed in adolescents with moderate‐to‐severe depression (P < 0.000), overweight and obese individuals (P < 0.002), girls (P < 0.038), and the 17‐ to 18‐year‐old age group (P < 0.007).

Conclusion

The data indicate that FA is positively associated with depression, obesity, age, and sex.
On a spectral problem in magnetohydrodynamics and its relevance for the geodynamo
Authors: Stefani Frank , Tretter Christiane
Published: October 2018

One of the most remarkable features of the geodynamo is the irregular occurrence of magnetic field reversals. Starting with the operator theoretical treatment of a non‐selfadjoint dynamo operator, we elaborate a dynamical picture of those reversals which relies on the existence of exceptional spectral points.
Geochronology and geochemistry of early Palaeozoic intrusive rocks in the Lajishan area of the eastern south Qilian Belt, Tibetan Plateau: Implications for the tectonic evolution of South Qilian
Authors: Cui Jiawei , Tian Liming , Sun Junyi , Yang Chao
Published: October 2018

The Lajishan area, located in the South Qilian orogenic Belt, north‐eastern Tibetan Plateau, contains a compositionally diverse range of Cambrian to early Ordovician felsic intrusions that reflect the early Palaeozoic tectonic evolution of the Central Qilian Belt. This paper presents new geochemical, Sr─Nd and Lu─Hf isotopic, and zircon U─Pb data for the Tadong, Huangcaoshan, and Yindonggou plutons in the eastern Lajishan area. LA‐ICPMS U─Pb ages of 517.4 ± 1 Ma for the Tadong pluton which is the first find Late Cambrian granitoids in this area, 467 ± 1 Ma for the Huangcaoshan pluton and 446 ± 1 Ma for the Yindonggou pluton. The new data indicate that the Tadong pluton and Huangcaoshan pluton belong to I‐type granite. Their A/CNK values range from 0.82 to 1.03, suggesting a close relationship with I‐type granitoids. Their trace‐element geochemical characteristics include enrichments in the LILEs, pronounced depletions in Nb and Ta, enrichment of the LREEs relative to the HREEs, and Eu anomalies. These features are similar to those of I‐type volcanic‐arc magmas. Combined with Hf and Sr─Nd isotopic data, The Tadong pluton generated by the mixing of melts was derived from the partial melting of the Precambrian basement and mantle‐derived magmas. The Huangcaoshan pluton was derived from juvenile crust with contamination. The Yindonggou pluton shows A‐type characteristics, their A/NCK is 0.88–1.07, and 10000 × Ga/Al is higher than 2.6. They were characteristic with high Sr, low Y, low Yb, and enriched LREE. Combined with Hf and Sr─Nd isotopic data, the Yindonggou pluton was generated by the partial melting of oceanic slab material and was crustally contaminated associated with slab breakoff. Combined previous research suggests that Tadong pluton and Huangcaoshan pluton formed from southern subduction of the South Qilian ocean into the Central Qilian Belt; the Yindonggou pluton formed in collisional setting.
Composition and U—Pb ages of apatite in the Amba Dongar carbonatite–alkaline complex, India
Authors: Fosu Benjamin R. , Ghosh Prosenjit , Chew David M. , Viladkar Shrinivas G.
Published: October 2018

The Amba Dongar carbonatite‐alkaline complex is regarded as a late phase intrusion (ca. 65 Ma) associated with Deccan volcanism. Existing age constraints on the Amba Dongar carbonatite are based on phlogopite 40Ar–39Ar plateau ages derived from carbonatite and associated alkaline rocks within the complex. We explore the utility of apatite, a common accessory mineral in Amba Dongar carbonatites, as a petrogenetic and geochronological tool to constrain further the evolution of the carbonatites. Apatite exhibits different crystal forms—from hexagonal stubby prisms to ovoid and elongate grains. Apatite occurs as cumulate and disseminated grains that are either primary, fractured, or recrystallized. SrO content is high in primary apatite (3.17 wt%) but less in recrystallized (1.90 wt%) and disseminated grains (0.47 wt%). MnO and Cl are negligible while FeO is typically low in all samples. SiO2 content is low except for a few primary grains which measure up to 1.35 wt%, correlating with high REE content. LREEs dominate the total REE budget of Amba Dongar apatite, with HREEs below EPMA detection limit in most samples. Total REE content is generally low, though some primary apatite contains up to 3.19 wt% REEs. We also report UPb apatite ages from the carbonatites analysed in situ by LA‐ICP‐MS. The data from all samples combined on a UPb Tera–Wasserburg concordia yield a lower intercept age of 65.4 ± 2.5 Ma (MSWD = 2.8, 207Pb/206Pbi = 0.8272 ± 0.0028), and the Amba Dongar carbonatites are thus interpreted to represent a phase of coeval magmatic activity with Deccan volcanism.