bluuebunny/crossref_metadata_2025 huggingface dataset:
Encoding of Self‐Referential Pain Catastrophizing in the Posterior Cingulate Cortex in Fibromyalgia
Authors: Lee Jeungchan , Protsenko Ekaterina , Lazaridou Asimina , Franceschelli Olivia , Ellingsen Dan‐Mikael , Mawla Ishtiaq , Isenburg Kylie , Berry Michael P. , Galenkamp Laura , Loggia Marco L. , Wasan Ajay D. , Edwards Robert R. , Napadow Vitaly
Published: March 2018

Objective

Pain catastrophizing is a common feature of chronic pain, including fibromyalgia (FM), and is strongly associated with amplified pain severity and disability. While previous neuroimaging studies have focused on evoked pain response modulation by catastrophizing, the brain mechanisms supporting pain catastrophizing itself are unknown. We designed a functional magnetic resonance imaging (fMRI)–based pain catastrophizing task whereby patients with chronic pain engaged in catastrophizing‐related cognitions. We undertook this study to test our hypothesis that catastrophizing about clinical pain would be associated with amplified activation in nodes of the default mode network (DMN), which encode self‐referential cognition and show altered functioning in chronic pain.

Methods

During fMRI, 31 FM patients reflected on how catastrophizing (CAT) statements (drawn from the Pain Catastrophizing Scale) impact their typical FM pain experience. Response to CAT statements was compared to response to matched neutral (NEU) statements.

Results

During statement reflection, higher fMRI signal during CAT statements than during NEU statements was found in several DMN brain areas, including the ventral (posterior) and dorsal (anterior) posterior cingulate cortex (vPCC and dPCC, respectively). Patients’ ratings of CAT statement applicability were correlated solely with activity in the vPCC, a main DMN hub supporting self‐referential cognition (r = 0.38, P < 0.05). Clinical pain severity was correlated solely with activity in the dPCC, a PCC subregion associated with cognitive control and sensorimotor processing (r = 0.38, P < 0.05).

Conclusion

These findings provide evidence that the PCC encodes pain catastrophizing in FM and suggest distinct roles for different PCC subregions. Understanding the brain circuitry encoding pain catastrophizing in FM will prove to be important in identifying and evaluating the success of interventions targeting negative affect in chronic pain management.
Exploring Orthogonal Hydrogen Bonding towards Designing Organic‐Salt‐Based Supramolecular Gelators: Synthesis, Structures, and Anticancer Properties
Authors: Chakraborty Poulami , Dastidar Parthasarathi
Published: March 2018

A series of primary ammonium monocarboxylate (PAM) salts derived from β‐alanine derivatives of pyrene and naphthalene acetic acid, along with the parent acids, were explored to probe the plausible role of orthogonal hydrogen bonding resulting from amide⋅⋅⋅amide and PAM synthons on gelation. Single‐crystal X‐ray diffraction (SXRD) studies were performed on two parent acids and five PAM salts in the series. The data revealed that orthogonal hydrogen bonding played an important role in gelation. Structure–property correlation based on SXRD and powder X‐ray diffraction data also supported the working hypothesis upon which these gelators were designed. 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) and cell migration assay on a highly aggressive human breast cancer cell line, MDA‐MB‐231, revealed that one of the PAM salts in the series, namely, PAA.B2, displayed anticancer properties, and internalization of the gelator salt in the same cell line was confirmed by cell imaging.
Alcohol‐Soluble Electron‐Transport Materials for Fully Solution‐Processed Green PhOLEDs
Authors: Chen Fudong , Wang Shirong , Xiao Yin , Peng Feng , Zhou Nonglin , Ying Lei , Li Xianggao
Published: March 2018

Two alcohol‐soluble electron‐transport materials (ETMs), diphenyl(4‐(1‐phenyl‐1H‐benzo[d]imidazol‐2‐yl)phenyl)phosphine oxide (pPBIPO) and (3,5‐bis(1‐phenyl‐1H‐benzo[d]imidazol‐2‐yl)phenyl)diphenylphosphine oxide (mBPBIPO), have been synthesized. The physical properties of these ETMs were investigated and they both exhibited high electron‐transport mobilities (1.67×10−4 and 2.15×10−4 cm2 V−1 s−1), high glass‐transition temperatures (81 and 110 °C), and low LUMO energy levels (−2.87 and −2.82 eV, respectively). The solubility of PBIPO in n‐butyl alcohol was more than 20 mg mL−1, which meets the requirement for fully solution‐processed organic light‐emitting diodes (OLEDs). Fully solution‐processed green‐phosphorescent OLEDs were fabricated by using alcohol‐soluble PBIPO as electron‐transport layers (ETLs), and they exhibited high current efficiencies, power efficiencies, and external quantum efficiencies of up to 38.43 cd A−1, 26.64 lm W−1, and 10.87 %, respectively. Compared with devices that did not contain PBIPO as an ETM, the performance of these devices was much improved, which indicated the excellent electron‐transport properties of PBIPO.
Simultaneous Achievement of Open and Closed Loop Diagonal Dominance Through Constant Feedback
Authors: Jetto Leopoldo , Orsini Valentina , Romagnoli Raffaele
Published: March 2018

This paper proposes a new and low complexity technique for the simultaneous achievement of open and closed loop diagonal dominance for uncertain plants. The method is based on the introduction of a static high gain inner feedback which modifies the plant to attain a diagonal dominant open loop compensated plant. The sufficient, easy to use, conditions derived for the open loop diagonal dominance also assure the simultaneous achievement of closed loop diagonal dominance under soft assumptions on the diagonal elements of the decoupled controller robustly stabilizing the plant. These assumptions agree with the usual closed‐loop performance specifications, so that closed‐loop diagonal dominance is achieved without any extra complication on the controller design procedure. The main merits of the present method are: applicability to uncertain plants, ease of implementation and low computational cost. Three examples taken from the relevant literature, are given to show the effectiveness of the proposed approach.
A New Way to Treat Brain Tumors: Targeting Proteins Coded by Microcephaly Genes?
Authors: Lang Patrick Y. , Gershon Timothy R.
Published: March 2018

New targets for brain tumor therapies may be identified by mutations that cause hereditary microcephaly. Brain growth depends on the repeated proliferation of stem and progenitor cells. Microcephaly syndromes result from mutations that specifically impair the ability of brain progenitor or stem cells to proliferate, by inducing either premature differentiation or apoptosis. Brain tumors that derive from brain progenitor or stem cells may share many of the specific requirements of their cells of origin. These tumors may therefore be susceptible to disruptions of the protein products of genes that are mutated in microcephaly. The potential for the products of microcephaly genes to be therapeutic targets in brain tumors are highlighted hereby reviewing research on EG5, KIF14, ASPM, CDK6, and ATR. Treatments that disrupt these proteins may open new avenues for brain tumor therapy that have increased efficacy and decreased toxicity.
A cytotoxicity, optical spectroscopy and computational binding analysis of 4‐[3‐acetyl‐5‐(acetylamino)‐2‐methyl‐2,3‐dihydro‐1,3,4‐thiadiazole‐2‐yl]phenyl benzoate in calf thymus DNA
Authors: Karthikeyan Subramani , Bharanidharan Ganesan , Mangaiyarkarasi Rajendiran , Chinnathambi Shanmugavel , Sriram Ragavan , Gunasekaran Krishnaswamy , Saravanan Kandasamy , Gopikrishnan Mani , Aruna Prakasarao , Ganesan Singaravelu
Published: March 2018

In this study the interaction mechanism between newly synthesized 4‐(3‐acetyl‐5‐(acetylamino)‐2‐methyl‐2, 3‐dihydro‐1,3,4‐thiadiazole‐2‐yl) phenyl benzoate (thiadiazole derivative) anticancer active drug with calf thymus DNA was investigated by using various optical spectroscopy techniques along with computational technique. The absorption spectrum shows a clear shift in the lower wavelength region, which may be due to strong hypochromic effect in the ctDNA and the drug. The results of steady state fluorescence spectroscopy show that there is static quenching occurring while increasing the thiadiazole drug concentration in the ethidium bromide‐ctDNA system. Also the binding constant (K), thermo dynamical parameters of enthalpy change (ΔH°), entropy change (ΔS°) Gibbs free energy change (ΔG°) were calculated at different temperature (293 K, 298 K) and the results are in good agreement with theoretically calculated MMGBSA binding analysis. Time resolved emission spectroscopy analysis clearly explains the thiadiazole derivative competitive intercalation in the ethidium bromide‐ctDNA system. Further, molecular docking studies was carried out to understand the hydrogen bonding and hydrophobic interaction between ctDNA and thiadiazole derivative molecule. In addition the docking and molecular dynamics charge distribution analysis was done to understand the internal stability of thiadiazole derivative drug binding sites of ctDNA. The global reactivity of thiadiazole derivative such as electronegativity, electrophilicity and chemical hardness has been calculated.
Physiological characterization and quantitative proteomic analyses of metabolically engineered E. coli K4 strains with improved pathways for capsular polysaccharide biosynthesis
Authors: Cimini Donatella , Russo Rosita , D'Ambrosio Sergio , Dello Iacono Ileana , Rega Camilla , Carlino Elisabetta , Argenzio Ottavia , Russo Luigi , D'Abrosca Brigida , Chambery Angela , Schiraldi Chiara
Published: March 2018

Among capsulated bacteria, some produce polysaccharides with unique properties that have been shown to possess relevant industrial applications and commercial value. The capsular polysaccharide (CPS) produced by Escherichia coli K4 is similar to chondroitin sulphate, and recent efforts focused on the development of genetic and fermentation strategies to increase its production titers up to technologically attractive levels. However, the control of the metabolic pathways leading to CPS synthesis together with the effect of varying the concentration of pathway intermediates on CPS final titers, is still quite unexplored, and not fully understood. In the present study four genes involved in the biosynthesis of UDP‐sugar CPS precursors, namely kfoA, kfoF, pgm, and galU, were overexpressed in different combinations, and diversely affected the biosynthetic machinery. At the physiological level, results revealed a central role for kfoF, coding for UDP‐glucose dehydrogenase, that increased CPS production mostly. In the attempt to unravel the molecular mechanisms regulating CPS biosynthesis, an in depth analysis of the proteome of the recombinant strains overexpressing respectively pgm and galU, and pgm, galU, and kfoF was performed and compared to the wild‐type. Although, interestingly, in both strains the impact of the genetic manipulation seemed rather limited at the proteome level, results obtained from the triple mutant indicated a crosstalk between the two pathways leading to UDP‐sugar precursors biosynthesis, and also an unexpected link with the purine biosynthetic pathway. Overall our results present new insights into the role of metabolic intermediates for the formation of capsular polysaccharides, utilizing a systematic approach of metabolic engineering, combined with state‐of‐the‐art quantitative proteomic approaches, as well as genetic and physiological information.
Optimization of bioprocess productivity based on metabolic‐genetic network models with bilevel dynamic programming
Authors: Jabarivelisdeh Banafsheh , Waldherr Steffen
Published: March 2018

One of the main goals of metabolic engineering is to obtain high levels of a microbial product through genetic modifications. To improve the productivity of such a process, the dynamic implementation of metabolic engineering strategies has been proven to be more beneficial compared to static genetic manipulations in which the gene expression is not controlled over time, by resolving the trade‐off between growth and production. In this work, a bilevel optimization framework based on constraint‐based models is applied to identify an optimal strategy for dynamic genetic and process level manipulations to increase productivity. The dynamic enzyme‐cost flux balance analysis (deFBA) as underlying metabolic network model captures the network dynamics and enables the analysis of temporal regulation in the metabolic‐genetic network. We apply our computational framework to maximize ethanol productivity in a batch process with Escherichia coli. The results highlight the importance of integrating the genetic level and enzyme production and degradation processes for obtaining optimal dynamic gene and process manipulations.
Follow-up after endovascular aortic aneurysm repair can be stratified based on first postoperative imaging
Authors: Baderkhan H , Haller O , Wanhainen A , Björck M , Mani K
Published: March 2018

Background

Lifelong postoperative surveillance is recommended following endovascular aneurysm repair (EVAR). Although the purpose is to prevent and/or identify complications early, it also results in increased cost and workload. This study was designed to examine whether it may be possible to identify patients at low risk of complications based on their first postoperative CT angiogram (CTA).

Methods

All patients undergoing EVAR in two Swedish centres between 2001 and 2012 were identified retrospectively and categorized based on the first postoperative CTA as at low risk (proximal and distal sealing zone at least 10 mm and no endoleak) or high risk (sealing zone less than 10 mm and/or presence of any endoleak) of complications.

Results

Some 326 patients (273 men) with a CTA performed less than 1 year after EVAR were included (low risk 212, 65·0 per cent; high risk 114, 35·0 per cent). There was no difference between the groups in terms of sex, age, co-morbidities, abdominal aortic aneurysm (AAA) diameter, preoperative AAA neck anatomy, stent-graft type or duration of follow-up (mean(s.d.) 4·8(3·2) years). Five-year freedom from AAA-related adverse events was 97·1 and 47·7 per cent in the low- and high-risk groups respectively (P < 0·001). The corresponding freedom from AAA-related reintervention was 96·2 and 54·1 per cent (P < 0·001). The method had a sensitivity of 88·3 per cent, specificity of 77·0 per cent and negative predictive value of 96·6 per cent to detect AAA-related adverse events. The number of surveillance imaging per AAA-related adverse event was 168 versus 11 for the low-risk versus high-risk group.

Conclusion

Two-thirds of patients undergoing EVAR have an adequate seal and no endoleak on the first postoperative CTA, and a very low risk of AAA-related events up to 5 years. Less vigilant follow-up after EVAR may be considered for these patients.
Serum carcinoembryonic antigen trends for diagnosing colorectal cancer recurrence in the FACS randomized clinical trial
Authors: Shinkins B , Primrose J N , Pugh S A , Nicholson B D , Perera R , James T , Mant D
Published: March 2018

Background

Most guidelines recommend that patients who have undergone curative resection for primary colorectal cancer are followed up for 5 years with regular blood carcinoembryonic antigen (CEA) tests to trigger further investigation for recurrence. However, CEA may miss recurrences, or patients may have false alarms and undergo unnecessary investigation.

Methods

The diagnostic accuracy of trends in CEA measurements for recurrent colorectal cancer, taken as part of the FACS (Follow-up After Colorectal Surgery) trial (2003–2014), were analysed. Investigation to detect recurrence was triggered by clinical symptoms, scheduled CT or colonoscopy, or a CEA level of at least 7 μg/l above baseline. Time-dependent receiver operating characteristic (ROC) curve analysis was used to compare the diagnostic accuracy of CEA trends with single measurements. CEA trends were estimated using linear regression.

Results

The area under the ROC curve (AUC) for CEA trend was at least 0·820 across all 5 years of follow-up. In comparison, the AUCs for single measurements ranged from 0·623 to 0·749. Improvement was most marked at the end of the first year of follow-up, with the AUC increasing from 0·623 (95 per cent c.i. 0·509 to 0·736) to 0·880 (0·814 to 0·947). However, no individual trend threshold achieved a sensitivity above 70 per cent (30 per cent missed recurrences).

Conclusion

Interpreting trends in CEA measurements instead of single CEA test results improves diagnostic accuracy for recurrence, but not sufficiently to warrant it being used as a single surveillance strategy to trigger further investigation. In the absence of a more accurate biomarker, monitoring trends in CEA should be combined with clinical, endoscopic and imaging surveillance for improved accuracy.
Large retrospective study of artificial dura substitute in patients with traumatic brain injury undergo decompressive craniectomy
Authors: Sun Hongtao , Wang Hongda , Diao Yunfeng , Tu Yue , Li Xiaohong , Zhao Wanyong , Ren Jibin , Zhang Sai
Published: March 2018

Background

Decompressive craniectomy is widely used for treating patients with traumatic brain injury (TBI). Usually patients have dura mater defect due to surgery or injury itself. The defective area may left open or repaired by artificial dura substitutes. A variety of artificial dura substitutes have been used for this purpose.

Objective

This study aimed to evaluate bovine‐derived pericardium membrane as artificial dural material for patients with decompressive craniectomy.

Methods

Totally 387 patients with severeTBIin our hospital were included in this study. Among them, 192 patients were treated with standard decompressive craniectomy without dura repair (control group). One hundred and ninety‐fiveTBIpatients were treated with dura repair by artificial dura materials (ADM). Nonlyophilized bovine pericardium membranes were used as artificial dura material. The postoperative complications were compared in both groups, including infection, seizure, and cerebrospinal fluid (CSF) leakage.

Results

Patients in control group have higher complication rates than patients inADMgroup, including subcutaneous hematoma (13.02% in control vs. 4.01% inADMgroup,p = .004), infection (12.5% in control vs. 5.64% inADMgroup,p = .021),CSFleakage (13.02% in control vs. 5.13% inADMgroup,p = .012), and seizure (10.42% in control vs. 3.08% inADMgroup,p = .007). Patients inADMgroup are only associated with higher incidence of foreign body reaction (6 of 195 patients inADMvs. none from control group).

Conclusion

Bovine‐derived pericardium membranes are successfully used as artificial dural substitutes for decompressive craniectomy. Patients withADMhave better clinical outcome than control group.
Variability in facial‐muscle innervation: A comparative study based on electrostimulation and anatomical dissection
Authors: De Bonnecaze G. , Vergez S. , Chaput B. , Vairel B. , Serrano E. , Chantalat E. , Chaynes P.
Published: March 2018

Facial‐nerve palsy is the most common complication during facial surgery. However, there are few detailed reports on the distribution of the terminal branches of the facial nerve to the mimetic muscles. This also applies to the communicating branches. The aim of our study was to assess the variability of communicant and terminal branches of the facial nerve in humans. This prospective study involved anatomical dissections and intraoperative electric stimulation of facial nerves. We first performed 30 dissections to define the branching patterns of the extracranial facial nerve, with particular focus on the penetrating points into the mimetic muscles. We then studied and compared these preliminary data with 14 operative facial stimulations conducted during parotidectomies. Each trunk and branch received systematic electrostimulation. The electrostimulation and facial‐and‐neck movements were analyzed by two independent reviewers. The peripheral branching and intercommunication of the facial branches were highly variable. Combining electrostimulation and dissections, the frontalis muscle, the depressor labii inferioris and the platysma showed little nerve recuperation whereas the sphincter muscles (orbicularis ori and oculi) were anatomically protected. Facial‐muscle innervation differed among individuals. We found complex variations in the facial branching mode. Our study highlights the branches and corresponding areas that could be considered anatomically risky. Clin. Anat. 32:169–175, 2019. © 2018 Wiley Periodicals, Inc.
Probing the Mint2 Protein–Protein Interaction Network Relevant to the Pathophysiology of Alzheimer's Disease
Authors: Jensen Thomas M. T. , Albertsen Louise , Bartling Christian R. O. , Haugaard‐Kedström Linda M. , Strømgaard Kristian
Published: March 2018

The intracellular adaptor protein Mint2 binds amyloid precursor protein (APP) and presenilin‐1, which are both central constituents of the amyloidogenic pathway associated with Alzheimer's disease (AD). Additional interaction partners have also been suggested for Mint2; several of them are also pertinent to AD pathogenesis. However, no comparative mapping of the Mint2 protein–protein interaction network is available. Here we provide a systematic characterization of seven interaction partners and address their specificities towards the different binding domains of Mint2, which reveal domain‐specific and ‐nonspecific interaction partners. Moreover, we show that the last two C‐terminal amino acids of Mint2 are both important for the intramolecular interaction with the PDZ1 domain and for the stability of Mint2.
Streptococcus pneumoniae as a cause of lactational mastitis: a case report
Authors: Hald Sara Vester , Schønheyder Henrik Carl
Published: March 2018

Key Clinical Message

Pneumococci are predominant in respiratory tract infections but may have unusual presentations such as lactational mastitis. We report a 29‐year‐old breastfeeding woman with pneumococcal mastitis confirmed by positive blood culture and culture of milk. Previously, a few similar cases have been reported, but none was associated with bacteremia.
Sevoflurane improves respiratory mechanics and gas exchange in a case series of infants with severe bronchiolitis‐induced acute respiratory distress syndrome
Authors: Nacoti Mirco , Colombo Jacopo , Fochi Oliviero , Bonacina Daniele , Fazzi Francesco , Bellani Giacomo , Bonanomi Ezio
Published: March 2018

Key Clinical Message

This report describes the successful use of a new intervention to improve respiratory mechanics and gas exchange in a relatively homogeneous group of infants with severe bronchiolitis‐induced PARDS after failure of conventional treatment. These results may open a new interesting area of research and management for PARDS patients.
Electrochemical Water Splitting by Pseudo‐spinel, Disordered and Layered Lithium Nickel Oxides: Correlation between Structural Motifs and Catalytic Properties
Authors: Wu Jian , Wang Guofu , Du Juan , Liu J. Ping , Wang Jianguo , Fan Weibin
Published: March 2018

In this work, three different structures of lithium nickel oxide (LNO) synthesized by simple methods as inexpensive and efficient electrocatalyst for OER were presented. The catalytic activities of LNO catalysts for OER were pseudo‐spinel (PS‐LiNiO2) > disordered (DO‐LiNiO2) > layered (L‐LiNiO2) lithium nickel oxide. Particularly, PS‐LiNiO2 demonstrated much lower tafel slope of 62 mV dec−1 with the highest durability whereas the layered LNO catalysts exhibited the higher tafel slope of 88 mV dec −1, respectively. To elucidate the origin of high activities of LNO catalysts, three structures of LNO were studied by EXAFS measurements and DFT theoretical calculation. Compared to L‐LiNiO2, PS‐LiNiO2, including Ni4O4 cubane structural motifs, exhibited higher valent states and lower Ni d‐band center to drive the catalytic reaction. Thus, our results demonstrated that the activities of LNO can be optimized by controlling the value states, chemical and local electronic structure of Ni via novel design approaches.
One‐Step Synthesis of NiCo2S4/Graphene Composite for Asymmetric Supercapacitors with Superior Performances
Authors: Yang Xue , Niu Hao , Jiang He , Sun Zhiqin , Wang Qian , Qu Fengyu
Published: March 2018

To meet the demand of high‐performance electrode materials for supercapacitors, it is highly desirable to design and develop a new class of electrode materials with superior electrochemical performance. Here, we used a simple hydrothermal method to synthesize NiCo2S4‐anchored graphene nanosheets (NiCo2S4/GNS) for high‐performance supercapacitors. Benefiting from the synergistic effect of graphene and NiCo2S4, the as‐prepared composite exhibits outstanding electrochemical performances, such as high specific capacitance (1063 F g−1 at current density of 2 A g−1) and excellent cycling performance while maintaining 82 % of the initial value after 10000 cycles. Furthermore, an asymmetric supercapacitor (ASC) is fabricated using NiCo2S4/GNS as positive electrode and nitrogen‐doped graphene as negative electrode. The fabricated ASC delivers a remarkable energy density of 54.6 Wh kg−1 at a power density of 350.8 W kg−1. The outstanding performances render such composite a promising candidate for application of high‐energy‐density supercapacitors.
Metal‐ and Reagent‐Free Anodic Dehydrogenative Cross‐Coupling of Naphthylamines with Phenols
Authors: Dahms Benedikt , Franke Robert , Waldvogel Siegfried R.
Published: March 2018

The front cover artwork is provided by the group of Siegfried R. Waldvogel at the Johannes Gutenberg‐Universität Mainz (Germany). The image depicts the electrochemical conversion of a phenolic substrate with a naphthylamine. Read the full text of the Communication at 10.1002/celc.201800050.
Partial least squares discriminant analysis for chemometrics and metabolomics: How scores, loadings, and weights differ according to two common algorithms
Authors: Brereton Richard G. , Lloyd Gavin R.
Published: March 2018

Two common algorithms for partial least squares discriminant analysis developed by Wold (NIPALS) and by Martens are compared. Although their classification performance is identical, their projections into variable space (often called scores) and into object space (loadings and weights) are quite different. Martens' algorithm can be visualised as a rotation in variable space, but Wold's results in quite complex distortions. Most software presents scores plots using the Wold algorithm but fails to appreciate that variable space is distorted, so scores from both algorithms are different. Weights, which can be obtained from both methods, are identical, although loadings (as commonly defined) from the Wold algorithm differ. The paper illustrates the two methods graphically to review the difference between these two methods.
Dative and Electron‐Sharing Bonding in C2F4
Authors: Andrada Diego M. , Casals‐Sainz José Luis , Martín Pendás Ángel , Frenking Gernot
Published: March 2018

The reaction pathway for the rupture of the carbon–carbon double bond of C2F4has been calculated with ab initio methods at the CASSCF(8,8)+NEVPT2/aug‐cc‐pVTZ and CCSD(T)/aug‐cc‐pVTZ levels and with density functional theory using M06‐L and M06‐2X functionals in conjunction with aug‐cc‐pVTZ basis sets. The calculations suggest that the bond dissociation pathway proceeds by a nonlinear reaction course without an activation barrier yielding the CF2fragments in the (1A1) ground state. A bonding analysis indicates that there is a continuous change in the electronic structure of the CF2fragments during the elongation of the C–C distance from a (3B1) excited state at the equilibrium geometry of C2F4to the (1A1) ground state. EDA‐NOCV calculations suggest that the carbon–carbon interactions in C2F4at equilibrium distance and longer C–C values up to ≈1.60 Å are best described in terms of electron‐sharing bonding between the CF2fragments in the (3B1) excited state. At longer distances, the situation changes toward dative bonding between CF2fragments in the (1A1) ground state.
Topology and Electronic Density Driven Generation of Alkali Cation Complexes
Authors: Boufroura Hamza , Poyer Salomé , Gaucher Anne , Huin Cécile , Salpin Jean‐Yves , Clavier Gilles , Prim Damien
Published: March 2018

The formation and characterization of K+ and Cs+ complexes originating from the cooperativity of three non‐covalent interactions is explored. The tridimensional preorganization of the naphthothiophene platform displays a favorable well‐defined bay region combining a π fragment and a carbonyl moiety flanking a central sulfur atom. A joint theoretical and experimental infrared multiple photon dissociation (IRMPD) study allowed deciphering the key contribution of the orthogonal phenyl fragment to the elaboration of alkali metal complexes. In combination with S and CO interactions, the π–cation interaction significantly enhances the binding energies of naphthothiophene derivatives.
Visible Light Activation of Spin‐Silenced Fluorescence
Authors: Eing Matthias , Tuten Bryan T. , Blinco James P. , Barner‐Kowollik Christopher
Published: March 2018

A self‐reporting, profluorescent, visible light‐induced release system is introduced. Fluorescence activation is enabled by a mild remote trigger signal that can be monitored with the naked‐eye in real time. The light‐responsive spin‐silenced polymer is synthesized via an Ugi post‐polymerization modification incorporating paramagnetic nitroxides and a light cleavable fluorophore moiety.
Investigation of Bistetramethylammonium Hydrogencyclotriphosphate—A Molecular Rotor?
Authors: Mangstl Martin , Weber Johannes , Jardón‐Álvarez Daniel , Burghaus Olaf , Roling Bernhard , Schmedt auf der Günne Jörn
Published: March 2018

The crystalline phase β‐[N(CH3)4]2HP3O9 undergoes a reversible phase transition to γ‐[N(CH3)4]2HP3O9, which was studied by dynamic scanning calorimetry and X‐ray diffraction. The rotational dynamics of the anion [P3O9]3− were evident from variable temperature 31P magic angle spinning (MAS) NMR spectroscopy. The rotational dynamics could be simulated with a 3‐site jump model, which yields spectra in good agreement with experiment. An activation energy of 0.6 eV could be estimated from line shape analysis. Impedance spectra reflect a bulk proton conductivity of γ‐[N(CH3)4]2HP3O9 of 6.9×10−5 S cm−1 at 240 °C and an activation energy of approximately 1.0 eV. Thus this salt features bulk protonic motion, while local rotational anionic motion happens with activation energies of the same order, as suggested by the paddle‐wheel mechanism.
Gold(I)‐Catalyzed Diastereo‐ and Enantioselective Synthesis of Polysubstituted Pyrrolo[3,4‐d][1,2]oxazines
Authors: Zhang Mei , Di Xiaoyu , Zhang Mingrui , Zhang Junliang
Published: March 2018

A gold(I)‐catalyzed highly diastereo‐ and enantioselective intermolecular cycloaddition of oxime ethers with nitrones under mild conditions was developed, which provides an facile access to optically pure highly substituted pyrrolo[3,4‐d][1,2]oxazines. The salient features of this reaction include general substrate scope, high efficiency, high enantioselectivity, readily available starting materials, and the use of commercially available ligand.
The impact of right ventricular function assessed by 2‐dimensional speckle tracking echocardiography on early mortality in patients with inferior myocardial infarction
Authors: Kanar Batur G. , Tigen Mustafa K. , Sunbul Murat , Cincin Altug , Atas Halil , Kepez Alper , Ozben Beste
Published: March 2018

Background

Right ventricular (RV) involvement in inferior myocardial infarction (MI) increases in‐hospital morbidity and mortality.

Hypothesis

RV systolic dysfunction assessed by 2‐dimensional speckle tracking echocardiography (STE) might be a predictor of early mortality in patients with acute inferior MI.

Methods

Eighty‐one consecutive patients with acute inferior MI (mean age, 60.8 ± 12.7 years; 18 females) were included. RV myocardial involvement was defined as an elevation >1 mm in V1 or V4R within 12 hours of symptom onset. RV function was assessed by STE. Patients were followed for 30 days for all‐cause mortality.

Results

Thirty‐eight patients had RV myocardial involvement, and they had significantly lower tricuspid annular plane systolic excursion (TAPSE), tricuspid annular systolic velocity (RVS), and left ventricular (LV) and RV global longitudinal strain (GLS). Nine patients (11%) died within 30 days. The mean age of mortality group was higher with more female frequency. They had significantly higher pro‐BNP, hs‐troponin T, and creatinine levels, but lower hemoglobin levels. TIMI 3 flow was significantly less achieved in mortality group. RV myocardial involvement was more frequent in the mortality group, and they had significantly lower TAPSE, RVS, and LV and RV GLS. Multivariate analysis revealed that age and RV GLS were independent predictors of early mortality. RV GLS ≤ –14% predicted early mortality in patients with acute inferior MI with a sensitivity of 88.9% and a specificity of 62.5% (AUC: 0.817, P = 0.002).

Conclusions

RV GLS may be useful in predicting early mortality in patients with acute inferior MI.
Obstacles to improving outcomes in the treatment of uveal melanoma
Authors: Tsai Katy K. , Bollin Kathryn B. , Patel Sapna P.
Published: March 2018

The rate of advances in uveal melanoma has not kept pace with the rate of advances in cutaneous melanoma. Many patients lack access to or knowledge of specialty centers, and integrated multidisciplinary care between ophthalmology, radiation oncology, and medical oncology is far from the norm. This treatment isolation leads to limited communication about novel clinical trial opportunities. Clinical trials themselves are not widely available, and a lack of robust funding limits rapid and complete investigations. This review outlines the obstacles to success in uveal melanoma management and highlights strategies for overcoming these challenges. Cancer 2018;124:2693‐2703. © 2018 American Cancer Society
Increased resource use in men with metastatic prostate cancer does not result in improved survival or quality of care at the end of life
Authors: Golan Ron , Bernstein Adrien N. , Gu Xiangmei , Dinerman Brian F. , Sedrakyan Art , Hu Jim C.
Published: March 2018

BACKGROUND

Cancer care and end‐of‐life (EOL) care contribute substantially to health care expenditures. Outside of clinical trials, to our knowledge there exists no standardized protocol to monitor disease progression in men with metastatic prostate cancer (mPCa). The objective of the current study was to evaluate the factors and outcomes associated with increased imaging and serum prostate‐specific antigen use in men with mPCa.

METHODS

Using Surveillance, Epidemiology, and End Results‐Medicare data from 2004 to 2012, the authors identified men diagnosed with mPCa with at least 6 months of follow‐up. Extreme users were classified as those who had either received prostate‐specific antigen testing greater than once per month, or who underwent cross‐sectional imaging or bone scan more frequently than every 2 months over a 6‐month period. Associations between extreme use and survival outcomes, costs, and quality of care at EOL, as measured by timing of hospice referral, frequency of emergency department visits, length of stay, and intensive care unit or hospital admissions, were examined.

RESULTS

Overall, a total of 3026 men with mPCa were identified, 791 of whom (26%) were defined as extreme users. Extreme users were more commonly young, white/non‐Hispanic, married, higher earning, and more educated (P<.001, respectively). Extreme use was not associated with improved quality of care at EOL. Yearly health care costs after diagnosis were 36.4% higher among extreme users (95% confidence interval, 27.4%‐45.3%; P<.001).

CONCLUSIONS

Increased monitoring among men with mPCa significantly increases health care costs, without a definitive improvement in survival nor quality of care at EOL noted. Monitoring for disease progression outside of clinical trials should be reserved for those in whom findings will change management. Cancer 2018;124:2212‐9. © 2018 American Cancer Society.
Long‐term outcome of relapsed acute promyelocytic leukemia treated with oral arsenic trioxide‐based reinduction and maintenance regimens: A 15‐year prospective study
Authors: Gill Harinder , Yim Rita , Lee Harold K. K. , Mak Vivien , Lin Shek‐Ying , Kho Bonnie , Yip Sze‐Fai , Lau June S. M. , Li Wah , Ip Ho‐Wan , Hwang Yu‐Yan , Chan Thomas S. Y. , Tse Eric , Au Wing‐Yan , Kumana Cyrus R. , Kwong Yok‐Lam
Published: March 2018

BACKGROUND

For patients who have acute promyelocytic leukemia (APL) in second complete remission (CR2), optimal postremission strategies remain undefined.

METHODS

The role of an oral arsenic trioxide (As2O3)‐based regimen in the management of patients who had APL in CR2 was examined.

RESULTS

Seventy‐three patients with APL in first relapse (R1) were studied. Oral As2O3‐based reinduction resulted uniformly in CR2, irrespective of previous As2O3 exposure. All patients received oral As2O3‐based maintenance in CR2. At a median follow‐up of 94 months (range, 9‐205 months), 43 patients (58.9%) were still in CR2, and 49 (67.1%) had finished the planned 2‐year CR2 maintenance with all‐trans retinoic acid, oral As2O3, and ascorbic acid. Reinduction and maintenance treatments were well tolerated. Grade 1 and 2 headache occurred in 20 patients (27.4%). Hepatotoxicity, all in the form of transaminitis, occurred in 35 patients (47.9%; grade 1 and 2, n = 26; grade 3 and 4, n = 9). Three patients had self‐limiting QTc prolongation. The 10‐year leukemia‐free survival rate was 56.8%. Thirty patients developed R2. Oral As2O3‐based reinduction led to CR3 in 27 patients (90%). Post‐CR3 strategies included autologous hematopoietic stem cell transplantation and oral As2O3 maintenance. At a post‐CR3 follow‐up of 30 months (range, 3‐166 months), 11 patients were still in CR3. The 5‐year and 10‐year overall survival rates in the R1 cohort were 79.5% and 67.3%, respectively. Prior receipt of oral As2O3 maintenance in CR1 was the only risk factor for inferior leukemia‐free survival. Central nervous system involvement occurred in 15 patients, including 5 who remained alive. Relapse during oral As2O3 therapy was the only significant risk factor for central nervous system involvement.

CONCLUSIONS

For patients with relapsed APL, As2O3 remained effective despite repeated As2O3 exposures. Oral As2O3 maintenance was an effective postremission strategy for CR2. Cancer 2018;124:2316‐26. © 2018 American Cancer Society.
Development of CNS metastases and survival in patients with inflammatory breast cancer
Authors: Uemura Marc I. , French John T. , Hess Kenneth R. , Liu Diane , Raghav Kanwal , Hortobagyi Gabriel N. , Arun Banu K. , Valero Vicente , Ueno Naoto T. , Alvarez Ricardo H. , Woodward Wendy A. , Debeb Bisrat G. , Moulder Stacy L. , Lim Bora , Tripathy Debu , Ibrahim Nuhad K.
Published: March 2018

BACKGROUND

Inflammatory breast cancer (IBC) is associated with a poor prognosis and high risk of central nervous system (CNS) metastases.

METHODS

We retrospectively reviewed stage III‐IBC patients compared with noninflammatory invasive ductal carcinoma (NI‐IDC) patients treated between January 1, 1984, and December 31, 2011, who began primary treatment within 1 year of diagnosis and had been followed up for at least 1 year before the development of CNS metastasis or death. Cumulative CNS metastasis incidence and post‐CNS metastasis overall survival (OS) estimates were computed. Multivariable Cox proportional hazard models explored factors for post‐CNS metastasis survival.

RESULTS

A total of 2323 patients were identified (589‐IBC/1734‐NI‐IDC). Eighty‐one IBC patients developed CNS metastasis, versus 154 NI‐IDC patients. The 2‐, 5‐, and 10‐year cumulative CNS metastasis incidence rates in IBC and NI‐IDC were 9.8%, 15.8%, 17.4% and 6.5%, 10.1%, and 12.7%, respectively. This was significantly different between IBC and NI‐IDC patients (P = .0037). Multicovariate competing risk regression models in IBC and NI‐IDC patients showed no statistically significant associations with the risk of developing CNS metastasis, except neoadjuvant taxane use in NI‐IDC patients (hazard ratio, 0.45; 95% confidence interval, 0.24‐0.83; P = .011). The median follow‐up was 7.2 years, and the median post‐CNS metastasis OS was not significantly different between IBC (7.6 months) and NI‐IDC (5.6 months) patients. One hundred ninety patients with CNS metastasis died. HER2‐positive patients had better OS, with a median 14.1 versus 4.3 months (P < .0001). Age >50 years (P = .012) but not IBC status was a significant predictor of post‐CNS metastasis survival.

CONCLUSION

IBC patients demonstrated higher CNS metastasis incidence rates but OS following CNS metastases is similar in both groups. HER2 status and age may play prognostic roles. Cancer 2018;124:2299‐305. © 2018 American Cancer Society.
Impact of the posttransplant lymphoproliferative disorder subtype on survival
Authors: Koff Jean L. , Li Jing‐Xia , Zhang Xinyan , Switchenko Jeffrey M. , Flowers Christopher R. , Waller Edmund K.
Published: March 2018

BACKGROUND

Posttransplant lymphoproliferative disorder (PTLD) is a life‐threatening complication of solid organ transplantation. Histologic heterogeneity and a lack of treatment standards have made evaluating clinical outcomes in specific patient populations difficult. This systematic literature review investigated the impact of the PTLD histologic subtype on survival in a large data set.

METHODS

Case series were identified on PubMed with the search terms post‐transplant lymphoproliferative disorder/disease, PTLD, and solid organ transplantation, with additional publications identified through reference lists. The patient characteristics, immunosuppressive regimen, treatment, survival, and follow‐up time for 306 cases were extracted from 94 articles, and these cases were combined with 11 cases from Emory University Hospital. Patients with a recorded subtype were included in a Kaplan‐Meier survival analysis (n = 234). Cox proportional hazards regression analyses identified predictors of overall survival (OS) for each subtype and B‐cell subgroup.

RESULTS

OS differed significantly between monomorphic T‐cell neoplasms (median, 9 months) and polymorphic, monomorphic B‐cell, and Hodgkin‐type neoplasms, for which the median OS was not reached (P = .0001). Significant differences in OS among B subgroups were not detected, but there was a trend toward decreased survival for patients with Burkitt‐type PTLD. Kidney transplantation and a reduction of immunosuppression were associated with increased OS for patients with B‐cell neoplasms in a multivariate analysis. Immunosuppression with azathioprine was associated with decreased OS for patients with T‐cell neoplasms, whereas radiotherapy was associated with improved OS for patients with that subtype.

CONCLUSIONS

The histologic subtype represents an important prognostic factor in PTLD, with patients with T‐cell neoplasms exhibiting very poor OS. Possibly lower survival for certain subsets of patients with B‐cell PTLD should be explored further and suggests the need for subtype‐specific therapies to improve outcomes. Cancer 2018;124:2327‐36. © 2018 American Cancer Society.
Association of externalizing religious and spiritual beliefs on stage of colon cancer diagnosis among black and white multicenter urban patient populations
Authors: Polite Blase N. , Cipriano‐Steffens Toni M. , Hlubocky Fay J. , Jean‐Pierre Pascal , Cheng Ying , Brewer Katherine C. , Rauscher Garth H. , Fitchett George A.
Published: March 2018

BACKGROUND

This study explores whether externalizing religious and spiritual beliefs is associated with advanced‐stage colon cancer at initial oncology presentation and whether this association is stronger for blacks than for whites.

METHODS

Patients who had newly diagnosed, invasive colon cancer were recruited at 9 sites in the Chicago metropolitan area. Eligible patients were non‐Hispanic white or black, ages 30 to 79 years, and diagnosed with a primary invasive colon cancer. Patients were interviewed on prior screening and diagnosis. Social and attitudinal constructs were measured, including the God Locus of Health Control (GLHC) and Religious Problem Solving. The final response rate was 52% and included 407 patients.

RESULTS

The median age was 59 years (range, 30‐79 years), and 51% of participants were black. Cancer stage was available for 389 (96%) patients and was divided between late stage (stages III‐IV; 60%) and early stage (stages I‐II; 40%). Multivariate analysis indicated that patients in the highest tertile of scores on the GLHC were more likely have an advanced stage of disease at presentation (odds ratio, 2.14; 95% confidence interval, 1.00‐4.59; P = .05) compared with those in the lowest tertile. No significant interaction was identified between race and GLHC scores for stage at presentation (P = .78).

CONCLUSIONS

In a large sample of black and white individuals across diverse health care systems, higher scores on the GLHC predicted late disease stage at presentation. Although blacks had significantly higher GLHC scores, race was not associated with stage at presentation, nor was the association between GLHC and stage limited to blacks. Further work is needed to better understand this association and to develop interventions to better connect the religious and health care spheres. Cancer 2018;124:2578‐87. © 2018 American Cancer Society.
Cost considerations for systemic therapy for patients with advanced genitourinary malignancies
Authors: Henry Mark A. , Leung Andrew , Filson Christopher P.
Published: March 2018

The rising cost of health care in the United States has been the focus of intense debate within the medical, legal, and legislative arenas, with the cost of cancer care representing an important component. Cost effectiveness is not always easy to define, and there is no standard metric in assessing this measure related to cancer therapies. Significant controversy surrounds exactly what is the appropriate cost per added year of life. This review examines cost, effectiveness, and comparative cost effectiveness of novel systemic therapies for patients with urologic malignancies. Cancer 2018;124:2897‐905. © 2018 American Cancer Society.