bluuebunny/crossref_metadata_2025 huggingface dataset:
Brief Report: Predicting Functional Disability: One‐Year Results From the Scottish Early Rheumatoid Arthritis Inception Cohort
Authors: Kronisch Caroline , McLernon David J. , Dale James , Paterson Caron , Ralston Stuart H. , Reid David M. , Tierney Ann , Harvie John , McKay Neil , Wilson Hilary E. , Munro Robin , Saunders Sarah , Richmond Ruth , Baxter Derek , McMahon Mike , Kumar Vinod , McLaren John , Siebert Stefan , McInnes Iain B. , Porter Duncan , Macfarlane Gary J. , Basu Neil
Published: February 2016

Objective

To identify baseline prognostic indicators of disability at 1 year within a contemporary early inflammatory arthritis inception cohort and then develop a clinically useful tool to support early patient education and decision‐making.

Methods

The Scottish Early Rheumatoid Arthritis (SERA) inception cohort is a multicenter, prospective study of patients with newly presenting RA or undifferentiated arthritis. SERA data were analyzed to determine baseline predictors of disability (defined as a Health Assessment Questionnaire [HAQ] score of ≥1) at 1 year. Clinical and psychosocial baseline exposures were entered into a forward stepwise logistic regression model. The model was externally validated using newly accrued SERA data and subsequently converted into a prediction tool.

Results

Of the 578 participants (64.5% female), 36.7% (n = 212) reported functional disability at 1 year. Functional disability was independently predicted by baseline disability (odds ratio [OR] 2.67 [95% confidence interval (95% CI) 1.98, 3.59]), depression (OR 2.52 [95% CI 1.18, 5.37]), anxiety (OR 2.37 [95% CI 1.33, 4.21]), being in paid employment with absenteeism during the last week (OR 1.19 [95% CI 0.63, 2.23]), not being in paid employment (OR 2.36 [95% CI 1.38, 4.03]), and being overweight (OR 1.61 [95% CI 1.04, 2.50]). External validation (using 113 newly acquired patients) evidenced good discriminative performance with a C statistic of 0.74, and the calibration slope showed no evidence of model overfit (P = 0.31).

Conclusion

In the context of modern early inflammatory arthritis treatment paradigms, predictors of disability at 1 year appear to be dominated by psychosocial rather than more traditional clinical measures. This indicates the potential benefit of early access to nonpharmacologic interventions targeting key psychosocial factors, such as mental health and work disability.
Association of Increased Treg Cell Levels With Elevated Indoleamine 2,3‐Dioxygenase Activity and an Imbalanced Kynurenine Pathway in Interferon‐Positive Primary Sjögren's Syndrome
Authors: Maria Naomi I. , van Helden‐Meeuwsen Cornelia G. , Brkic Zana , Paulissen Sandra M. J. , Steenwijk Eline C. , Dalm Virgil A. , van Daele Paul L. , Martin van Hagen P. , Kroese Frans G. M. , van Roon Joel A. G. , Harkin Andrew , Dik Willem A. , Drexhage Hemmo A. , Lubberts Erik , Versnel Marjan A.
Published: February 2016

Objective

Indoleamine 2,3‐dioxygenase (IDO), the rate‐limiting enzyme that converts tryptophan to kynurenine, is driven in part by type I and type II interferons (IFNs). Naive T cells are polarized into FoxP3+ Treg cells upon exposure to either IDO+ cells or kynurenine. Recent studies have suggested that the kynurenine pathway reflects a crucial interface between the immune and nervous system. The aims of the present study were to evaluate whether Treg cell levels are elevated, in conjunction with increased IDO activity, in patients with primary Sjögren's syndrome (SS) who are positive for the IFN gene expression signature, and to investigate the downstream kynurenine pathway in these patients.

Methods

Serum from 71 healthy controls, 58 IFN‐negative patients with primary SS, and 66 IFN‐positive patients with primary SS was analyzed using high‐performance liquid chromatography to measure the levels of tryptophan and kynurenine. Expression levels of messenger RNA (mRNA) for IDO and downstream enzymes in the kynurenine pathway were assessed in CD14+ monocytes using real‐time quantitative polymerase chain reaction. CD4+CD45RO+ T helper memory cell populations were analyzed by flow cytometry.

Results

Significantly increased levels of IDO activity (assessed as the kynurenine:tryptophan ratio) (P = 0.0054) and percentages of CD25highFoxP3+ Treg cells (P = 0.039) were observed in the serum from IFN‐positive patients with primary SS, and these parameters were significantly correlated with one another (r = 0.511, P = 0.002). In circulating monocytes from IFN‐positive patients with primary SS, the expression of IDO1 mRNA was up‐regulated (P < 0.0001), and this was correlated with the IFN gene expression score (r = 0.816, P < 0.0001). Interestingly, the proapoptotic and neurotoxic downstream enzyme kynurenine 3‐monooxygenase was up‐regulated (P = 0.0057), whereas kynurenine aminotransferase I (KATI) (P = 0.0003), KATIII (P = 0.016), and KATIV (P = 0.04) were down‐regulated in IFN‐positive patients with primary SS compared to healthy controls.

Conclusion

These findings demonstrate enhanced IDO activity in conjunction with increased percentages of CD25highFoxP3+ Treg cells in primary SS patients who carry the IFN signature. In addition, IFN‐positive patients with primary SS exhibit an imbalanced kynurenine pathway, with evidence of a shift toward potentially more proapoptotic and neurotoxic metabolites. Intervening in these IFN‐ and IDO‐induced immune system imbalances may offer a new array of possibilities for therapeutic interventions in patients with primary SS.
Associations of Smoking and Age With Inflammatory Joint Signs Among Unaffected First‐Degree Relatives of Rheumatoid Arthritis Patients: Results From Studies of the Etiology of Rheumatoid Arthritis
Authors: Sparks Jeffrey A. , Chang Shun‐Chiao , Deane Kevin D. , Gan Ryan W. , Kristen Demoruelle M. , Feser Marie L. , Moss LauraKay , Buckner Jane H. , Keating Richard M. , Costenbader Karen H. , Gregersen Peter K. , Weisman Michael H. , Mikuls Ted R. , O'Dell James R. , Michael Holers V. , Norris Jill M. , Karlson Elizabeth W.
Published: February 2016

Objective

To examine whether genetic, environmental, and serologic rheumatoid arthritis (RA) risk factors are associated with inflammatory joint signs in a cohort of first‐degree relatives (FDRs) of RA patients.

Methods

We evaluated RA risk factors and inflammatory joint signs in a prospective cohort of FDRs without RA in the Studies of the Etiology of RA. Genetic factors included 5 HLA–DRB1 shared epitope alleles and 45 RA‐associated single‐nucleotide polymorphisms; loci were combined using genetic risk scores weighted by RA risk. Environmental factors (smoking, body mass index, education, and parity) and RA‐related autoantibodies were assessed at baseline. Physical examination was performed at baseline and 2‐year follow‐up, by observers who were blinded with regard to autoantibody status, to assess inflammatory joint signs as tender or swollen joints at sites typical for RA. Logistic regression was performed to evaluate associations of genetic, environmental, and serologic factors with inflammatory joint signs.

Results

We analyzed 966 non‐Hispanic white FDRs at baseline and 262 at 2‐year follow‐up after excluding those with inflammatory joint signs at baseline. The mean ± SD age was 47.2 ± 15.5 years, 71% were female, and 55% were shared epitope positive. Smoking >10 pack‐years was associated with inflammatory joint signs at baseline (odds ratio [OR] 1.89 [95% confidence interval (95% CI) 1.26–2.82]) and at 2 years (OR 2.66 [95% CI 1.01–7.03]), compared to never smokers. There was a significant interaction between smoking and age with regard to risk of inflammatory joint signs (P = 0.02). FDRs younger than 50 years with >10 pack‐years had the highest risk of inflammatory joint signs (OR 4.39 [95% CI 2.22–8.66], compared to never smokers younger than 50 years).

Conclusion

In a high‐risk cohort of FDRs, smoking and age were associated with both prevalent and incident inflammatory joint signs at sites typical for RA. Further prospective investigations of the factors affecting the transitions between preclinical RA phases are warranted.
Amine‐bis(phenolate) Iron(III)‐Catalyzed Formal Hydroamination of Olefins
Authors: Zhu Kailong , Shaver Michael P. , Thomas Stephen P.
Published: February 2016

A practical synthesis of highly functionalized amines by the formal hydroamination reaction of alkenes with nitroarenes catalyzed by an air stable amine‐bis(phenolate) iron(III) complex is reported. The reaction uses an easily handled silane, low catalyst loadings, and mild reaction conditions. A wide range of substrates are transformed with synthetically useful yields (21 examples).
An Enantioselective Assembly of Dihydropyranones through an NHC/LiCl‐Mediated in situ Activation of α,β‐Unsaturated Carboxylic Acids
Authors: Que Yonglei , Lu Yinan , Wang Wenjing , Wang Yuhong , Wang Haotian , Yu Chenxia , Li Tuanjie , Wang Xiang‐Shan , Shen Shide , Yao Changsheng
Published: February 2016

A straightforward N‐heterocyclic carbene (NHC)/LiCl‐mediated synthesis of dihydropyranones from α,β‐unsaturated carboxylic acids and 1,3‐dicarbonyl compounds was realized through the in situ activation strategy. The key advantages of this protocol include ready availability and high stability of starting materials, good yields, and excellent enantioselectivity.
Structure‐Triggered High Quantum Yield Luminescence and Switchable Dielectric Properties in Manganese(II) Based Hybrid Compounds
Authors: Wang Zhong‐Xia , Li Peng‐Fei , Liao Wei‐Qiang , Tang Yuanyuan , Ye Heng‐Yun , Zhang Yi
Published: February 2016

Two new manganese(II) based organic–inorganic hybrid compounds, C11H21Cl3MnN2 (1) and C11H22Cl4MnN2 (2), with prominent photoluminescence and dielectric properties were synthesized by solvent modulation. Compound 1 with novel trigonal bipyramidal geometry exhibits bright red luminescence with a lifetime of 2.47 ms and high quantum yield of 35.8 %. Compound 2 with tetrahedral geometry displays intense long‐lived (1.54 ms) green light emission with higher quantum yield of 92.3 %, accompanied by reversible solid‐state phase transition at 170 K and a distinct switchable dielectric property. The better performance of 2 results from the structure, including a discrete organic cation moiety and inorganic metal anion framework, which gives the cations large freedom of motion.
Reactions of a Ruthenium Complex with Substituted N‐Propargyl Pyrroles
Authors: Chia Pi‐Yeh , Huang Shou‐Ling , Liu Yi‐Hong , Lin Ying‐Chih
Published: February 2016

In an investigation into the chemical reactions of N‐propargyl pyrroles 1 a–c, containing aldehyde, keto, and ester groups on the pyrrole ring, with [Ru]−Cl ([Ru]=Cp(PPh3)2Ru; Cp=C5H5), an aldehyde group in the pyrrole ring is found to play a crucial role in stimulating the cyclization reaction. The reaction of 1 a, containing an aldehyde group, with [Ru]−Cl in the presence of NH4PF6 yields the vinylidene complex 2 a, which further reacts with allyl amine to give the carbene complex 6 a with a pyrrolizine group. However, if 1 a is first reacted with allyl amine to yield the iminenyne 8 a, then the reaction of 8 a with [Ru]−Cl in the presence of NH4PF6 yields the ruthenium complex 9 a, containing a cationic pyrrolopyrazinium group, which has been fully characterized by XRD analysis. These results can be adequately explained by coordination of the triple bond of the propargyl group to the ruthenium metal center first, followed by two processes, that is, formation of a vinylidene intermediate or direct nucleophilic attack. Additionally, the deprotonation of 2 a by R4NOH yields the neutral acetylide complex 3 a. In the presence of NH4PF6, the attempted alkylation of 3 a resulted in the formation the Fischer‐type amino–carbene complex 5 a as a result of the presence of NH3, which served as a nucleophile. With KPF6, the alkylation of 3 a with ethyl and benzyl bromoacetates afforded the disubstituted vinylidene complexes 10 a and 11 a, containing ester groups, which underwent deprotonation reactions to give the furyl complexes 12 a and 13 a, respectively. For 13 a, containing an O‐benzyl group, subsequent 1,3‐migration of the benzyl group was observed to yield product 14 a with a lactone unit. Similar reactivity was not observed for the corresponding N‐propargyl pyrroles 1 b and 1 c, which contained keto and ester groups, respectively, on the pyrrole ring.
Solution and Solid‐State Analysis of Binding of 13‐Substituted Berberine Analogues to Human Telomeric G‐quadruplexes
Authors: Ferraroni Marta , Bazzicalupi Carla , Papi Francesco , Fiorillo Gaetano , Guamán‐Ortiz Luis Miguel , Nocentini Alessio , Scovassi Anna Ivana , Lombardi Paolo , Gratteri Paola
Published: February 2016

The interaction between 13‐phenylalkyl and 13‐diphenylalkyl berberine derivatives (NAX) and human telomeric DNA G4 structures has been investigated by both spectroscopic and crystallographic methods. NAX042 and NAX053 are the best compounds improving the performance of the natural precursor berberine. This finding is in agreement with the X‐ray diffraction result for the NAX053‐Tel12 adduct, showing the ligand which interacts via π‐stacking, sandwiched at the interface of two symmetry‐related quadruplex units, with its benzhydryl group contributing to the overall stability of the adduct by means of additional π‐stacking interactions with the DNA residues. The berberine derivatives were also investigated for their cytotoxic activity towards a panel of human cancer cell lines. Compounds NAX042 and NAX053 affect the viability of cancer cell lines in a dose‐dependent manner.
Effects of Performance Criteria during Reading Instruction on Generalized Oral Reading Fluency
Authors: Young Nicholas D. , Daly Edward J.
Published: February 2016

Although there is some evidence that setting performance criteria may improve oral reading fluency interventions, little is known about the generalized effects of these criteria. The present study trained two third‐grade students to three different fluency levels on instructional passages and assessed generalized performance in corresponding high word‐overlap passages within an alternating treatments design. Results indicated no discernable differences across experimental conditions. Follow‐up analyses revealed that generalized gains per trial were actually larger in lower criterion conditions, suggesting that performance criteria may not be as helpful as previously thought. The results are discussed in terms of the need to empirically investigate the number of instructional trials necessary to maximize instructional efficiency. Copyright © 2016 John Wiley & Sons, Ltd.
A Review of Behavioral Interventions for Anxiety‐Related Behaviors in Lower‐Functioning Individuals with Autism
Authors: Rosen Tamara E. , Connell James E. , Kerns Connor M.
Published: February 2016

Anxiety is highly prevalent in persons with autism and affects individuals with higher‐functioning autism (HFA) and lower‐functioning autism (LFA). Although there is emerging support for the efficacy of cognitive‐behavioral therapy (CBT) in treating anxiety in autism, these findings are largely based on HFA samples. Moreover, CBT may be inappropriate for individuals with LFA who may struggle to grasp the cognitive components of the therapy because of their more limited verbal abilities. Behavior analytic interventions may be better suited to treat anxiety in this population; however, the quantity and quality of the extant literature have yet to be reviewed. Toward this end, the extant behavioral intervention literature was reviewed. Seven studies met the inclusion criteria and were evaluated against quality indicators for within‐subject design research. Next, the efficacy of each treatment component was assessed using established criteria for defining empirically supported therapies. Results revealed behavioral interventions to be efficacious, with desensitization and reinforcement emerging as efficacious treatment components, while prompting, modeling, and antianxiety stimuli were established as possibly efficacious. However, given that some of the quality indicators were not met, these results should be interpreted with some caution. Additional research is needed to form a more conclusive evidence base for the treatment of anxiety in individuals with LFA. Copyright © 2016 John Wiley & Sons, Ltd.
Practical guide to the Idea, Development and Exploration stages of the IDEAL Framework and Recommendations
Authors: Pennell C P , Hirst A D , Campbell W B , Sood A , Agha R A , Barkun J S T , McCulloch P
Published: February 2016

Background

Evaluation of new surgical procedures is a complex process challenged by evolution of technique, operator learning curves, the possibility of variable procedural quality, and strong treatment preferences among patients and clinicians. Preliminary studies that address these issues are needed to prepare for a successful randomized trial. The IDEAL (Idea, Development, Exploration, Assessment and Long-term follow-up) Framework and Recommendations provide an integrated step-by-step evaluation pathway that can help investigators achieve this.

Methods

A practical guide was developed for investigators evaluating new surgical interventions in the earlier phases before a randomized trial (corresponding to stages 1, 2a and 2b of the IDEAL Framework). The examples and practical tips included were chosen and agreed upon by consensus among authors with experience either in designing and conducting IDEAL format studies, or in helping others to design such studies. They address the most common challenges encountered by authors attempting to follow the IDEAL Recommendations.

Results

A decision aid has been created to help identify the IDEAL stage of an innovation from literature reports, with advice on how to design and report the IDEAL study formats discussed, along with the ethical and scientific rationale for specific recommendations.

Conclusion

The guide helps readers and researchers to understand and implement the IDEAL Framework and Recommendations to improve the quality of evidence supporting surgical innovation.
Regioselective deprotection of the monosaccharide‐bearing thiocyanomethyl group at the anomeric position monitored by reversed‐phase HPLC method
Authors: Abualassal Qais , Al Azzam Khaldun M. , Jilani Jamal A.
Published: February 2016

In the current work, the investigation and development of a chemo‐enzymatic approach for the synthesis of neo‐glycoproteins have been studied. This strategy is based on the regioselective enzymatic hydrolysis of peracetylated monosaccharide, functionalized at the anomeric position (C1) as 1‐thio‐(S‐cyanomethyl) group, a precursor of the 2‐ iminomethoxyethyl thioglycosides‐linker for protein glycosylation, catalyzed by immobilized enzymes to obtain selectively monodeprotected compounds. The use of this activation in C1 is the most frequently used strategy for glycoprotein preparation. The selected biocatalysts are the lipase from Candida rugosa and the acetyl xylan esterase from Bacillus pumilus. A reversed‐phase high‐performance liquid‐chromatographic (HPLC) method for monitoring the regioselective deprotection reaction has been developed. The developed HPLC method was used as a fingerprint to follow the hydrolysis of substrate 1 to substrate 1a and to determine its purity and yield. Moreover, the obtained compound was further purified by flash chromatography. The obtained compound 1a was further characterized using 1H, 13C NMR, correlation spectroscopy (COSY) and heteronuclear multiple bond correlation. The resulting product can be used as an intermediate for the preparation of di‐ and more complex oligosaccharides aimed at protein conjugation. Copyright © 2016 John Wiley & Sons, Ltd.
Determination and validation of chikusetsusaponin IVa in rat plasma by UPLC‐MS/MS and its application to pharmacokinetic study
Authors: Wang Ying , Liu Shi‐Ping , Guo Mei‐Hua , Wang Zhuo
Published: February 2016

A novel, sensitive and rapid ultra‐performance liquid chromatography–tandem mass spectrometric method for the quantification of chikusetsusaponin IVa (CHS‐IVa) in rat plasma was established and validated. Plasma samples were pre‐treated by precipitation of protein with acetonitrile and chromatographed on a Waters Symmetry C18 analytical column (4.6 × 50 mm, i.d., 3.5 μm) using a mobile phase consisting of methanol and water containing 0.05% formic acid (55:45, v/v) at a flow rate of 0.4 mL/min. The deprotonated molecular ions [M − H]– were employed in electrospray negative ionization mode and selected reaction monitoring transitions were performed for detection. The calibration curves exhibited good linearity (r > 0.99) over the range of 0.5–1000 ng/mL for CHS‐IVa. The recoveries of CHS‐IVa were >92.5% and exhibited no severe matrix effect. This method was successfully applied in the pharmacokinetic study of CHS‐IVa in rats. For oral administration, the plasma concentrations of CHS‐IVa increased to a peak value at 0.35 ± 0.14 h, followed by a gradual decrease to the lower limit of quantitation in 24 h. For intravenous administration, the plasma concentrations of CHS‐IVa decreased quickly (t1/2, 1.59 ± 0.25 h). The absolute bioavailability of CHS‐IVa in rats was 8.63%. Copyright © 2016 John Wiley & Sons, Ltd.
Correctors Rescue CFTR Mutations in Nucleotide‐Binding Domain 1 (NBD1) by Modulating Proteostasis
Authors: Lopes‐Pacheco Miquéias , Sabirzhanova Inna , Rapino Daniele , Morales Marcelo M. , Guggino William B. , Cebotaru Liudmila
Published: February 2016

We evaluated whether small molecule correctors could rescue four nucleotide‐binding domain 1 (NBD1) mutations in the cystic fibrosis transmembrane conductance regulator (CFTR) gene (A455E, S492F, ΔI507, and R560T). We first transfected Cos‐7 cells (green monkey kidney cells) with A455E, S492F, ΔI507, or R560T and created HEK‐293 (human embryonic kidney cells) cell lines stably expressing these CFTR mutations. The mutants showed lowered protein expression, instability at physiological temperature, and rapid degradation. After treatment with correctors CFFT‐002, CFFT‐003, C3, C4, and/or C18, the combination of C18+C4 showed the most correction and resulted in increased CFTR residing in the plasma membrane. We found a profound decrease in binding of CFTR to histone deacetylases (HDAC) 6 and 7 and heat shock proteins (Hsps) 27 and 40. Silencing Hsp27 or 40 rescued the mutants, but no additional amount of CFTR was rescued when both proteins were knocked down simultaneously. Thus, CFTR mutations in NBD1 can be rescued by a combination of correctors, and the treatment alters the interaction between mutated CFTR and the endoplasmic reticulum machinery.
Biomedical Applications of DNA‐Conjugated Gold Nanoparticles
Authors: Wang Chun‐Chi , Wu Shou‐Mei , Li Hung‐Wen , Chang Huan‐Tsung
Published: February 2016

Gold nanoparticles (AuNPs) are useful for diagnostic and biomedical applications, mainly because of their ease in preparation and conjugation, biocompatibility, and size‐dependent optical properties. However, bare AuNPs do not possess specificity for targets. AuNPs conjugated with DNA aptamers offer specificity for various analytes, such as proteins and small molecules/ions. Although DNA aptamers themselves have therapeutic and target‐recognizing properties, they are susceptible to degradation in vivo. When DNA aptamers are conjugated to AuNPs, their stability and cell uptake efficiency both increase, making aptamer–AuNPs suitable for biomedical applications. Additionally, drugs can be efficiently conjugated with DNA aptamer–AuNPs to further enhance their therapeutic efficiency. This review focuses on the applications of DNA aptamer‐based AuNPs in several biomedical areas, including anticoagulation, anticancer, antibacterial, and antiviral applications.
Murder and psychosis: Neuropsychological profiles of homicide offenders with schizophrenia
Authors: Stratton John , Brook Michael , Hanlon Robert E.
Published: February 2016

Background

Neurocognitive dysfunction, a core feature of schizophrenia, is thought to contribute to the impulsive violent aggression manifested by some individuals with schizophrenia, but not enough is known about how homicidal individuals with schizophrenia perform on neuropsychological measures.

Aims

The primary aim of our study was to describe the neuropsychological profiles of homicide offenders with schizophrenia. Supplementary analyses compared the criminal, psychiatric and neuropsychological features of schizophrenic homicide offenders with and without God/Satan/demon‐themed psychotic symptoms.

Methods

Twenty‐five men and women diagnosed with schizophrenia who had killed another person – 21 convicted of first‐degree murder and 4 found not guilty by reason of insanity – completed neuropsychological testing during forensic evaluations.

Results

The sample was characterised by extensive neurocognitive impairments, involving executive dysfunction (60%), memory dysfunction (68%) and attentional dysfunction (50%), although those with God/Satan/demon‐themed psychotic symptoms performed better than those with nonreligious psychotic content.

Conclusions

Our findings indicate that impaired cognition may play an important role in the commission of homicide by individuals with schizophrenia. A subgroup with God/Satan/demon delusions seem sufficiently less impaired that they might be able to engage in metacognitive treatment approaches, aimed at changing their relationship to their psychotic symptoms, thus reducing the perception of power and omnipotence of hallucinated voices and increasing their safety. Copyright © 2016 John Wiley & Sons, Ltd.
Hydrogenation of Condensed Aromatic Compounds over Mesoporous Bifunctional Catalysts Following a Diels–Alder Adduct Pathway
Authors: Huyen Pham Thanh , Krivec Marko , Kočevar Marijan , Bucur Ioana C. , Rizescu Cristina , Parvulescu Vasile I.
Published: February 2016

Pt(0.5 wt %)‐Al‐SBA‐15 and Pt(0.5 wt %)‐Al‐MCM‐41 bifunctional catalysts were prepared by wet impregnation and investigated in the hydrogenation of anthracene and the hydrogenolysis/hydrogenation of a series of synthesized Diels–Alder adducts with anthracene and anthracene derivatives. The mesoporous texture of the investigated catalysts allowed the hydrogenation of these substrates to a large extent. In direct correlation with the size of the Pt particles, Pt‐Al‐SBA‐15 exhibited a higher activity. Both catalysts exhibited a strong Lewis acidity associated with the presence of the Al extra‐framework species. The acidity of these catalysts afforded the esterification of the reaction byproduct, that is, succinic anhydride, with methanol or ethanol, and the hydrocracking/decyclization of one hydrogenated ring to lead to 1,2,3,4‐tetrahydronaphthalene derivatives. A good correlation with the calculated values of the reaction Gibbs free energy has been evidenced.
Sustainable Strategy Utilizing Biomass: Visible‐Light‐Mediated Synthesis of γ‐Valerolactone
Authors: Verma Sanny , Baig R. B. Nasir , Nadagouda Mallikarjuna N. , Varma Rajender S.
Published: February 2016

A novel sustainable approach to valued γ‐valerolactone was investigated. This approach exploits the visible‐light‐mediated conversion of biomass‐derived levulinic acid by using a bimetallic catalyst on a graphitic carbon nitride, AgPd@g‐C3N4.
Syngas Production via Reverse Water‐Gas Shift Reaction over a Ni‐Al2O3 Catalyst: Catalyst Stability, Reaction Kinetics, and Modeling
Authors: Wolf Andreas , Jess Andreas , Kern Christoph
Published: February 2016

The synthesis of liquid fuels from CO2, e.g., separated from flue gases of power plants, and H2 from renewables, i.e., water electrolysis, is a concept for substituting fossil fuels in the transport sector. It consists of two steps, syngas production via reverse water‐gas shift (RWGS) and synfuel production by Fischer‐Tropsch synthesis. Research is concentrated on the RWGS using a Ni‐catalyst. The catalyst shows an appropriate performance in catalyzing the RWGS. The catalyst is stable at technically relevant temperatures. The intrinsic and effective kinetics were determined and considerations on a technical application of the process are proposed.
Palladium Supported on Carbon Nanotubes for Methane Catalytic Oxidation
Authors: Gao Xiuhui , Wang Sheng , Gao Diannan , Chen Zhiping , Liu Weigang , Wang Mingzhe , Wang Shudong
Published: February 2016

A series of palladium/multi‐walled carbon nanotube (Pd/MWCNT) catalysts were prepared for the total oxidation of methane. Their morphologies, thermal stabilities and redox properties were investigated using different analytical techniques. Their textural properties were also measured by the Brunauer‐Emmett‐Teller method. On this basis, the catalytic behaviors were tailored by pretreating with mixed acid solutions and changing the MWCNT diameters. The results show that higher MWCNT diameters improved the Pd dispersion and enhanced the catalytic properties of the Pd/MWCNT. A proper ratio of HNO3 to H2SO4 can provide moderately active sites such as oxygen‐containing groups (OCG) and defects, on which the Pd precursor can be attached or anchored. Excessive H2SO4 will deteriorate the carbon framework and lower the frequency of OCG decorated on the outer surface of the MWCNT. As a result, the activity of the Pd/MWCNT catalysts for methane oxidation is suppressed.
One‐Pot Synthesis of CoSex–rGO Composite Powders by Spray Pyrolysis and Their Application as Anode Material for Sodium‐Ion Batteries
Authors: Park Gi Dae , Kang Yun Chan
Published: February 2016

A simple one‐pot synthesis of metal selenide/reduced graphene oxide (rGO) composite powders for application as anode materials in sodium‐ion batteries was developed. The detailed mechanism of formation of the CoSex–rGO composite powders that were selected as the first target material in the spray pyrolysis process was studied. The crumple‐structured CoSex–rGO composite powders prepared by spray pyrolysis at 800 °C had a crystal structure consisting mainly of Co0.85Se with a minor phase of CoSe2. The bare CoSex powders prepared for comparison had a spherical shape and hollow structure. The discharge capacities of the CoSex–rGO composite and bare CoSex powders in the 50th cycle at a constant current density of 0.3 A g−1 were 420 and 215 mA h g−1, respectively, and their capacity retentions measured from the second cycle were 80 and 46 %, respectively. The high structural stability of the CoSex–rGO composite powders for repeated sodium‐ion charge and discharge processes resulted in superior sodium‐ion storage properties compared to those of the bare CoSex powders.
Chemically Stable Covalent Organic Framework (COF)‐Polybenzimidazole Hybrid Membranes: Enhanced Gas Separation through Pore Modulation
Authors: Biswal Bishnu P. , Chaudhari Harshal D. , Banerjee Rahul , Kharul Ulhas K.
Published: February 2016

Highly flexible, TpPa‐1@PBI‐BuI and TpBD@PBI‐BuI hybrid membranes based on chemically stable covalent organic frameworks (COFs) could be obtained with the polymer. The loading obtained was substantially higher (50 %) than generally observed with MOFs. These hybrid membranes show an exciting enhancement in permeability (about sevenfold) with appreciable separation factors for CO2/N2 and CO2/CH4. Further, we found that with COF pore modulation, the gas permeability can be systematically enhanced.
Rapid Preparation of Silsesquioxane‐Based Ionic Liquids
Authors: Li Liguo , Liu Hongzhi
Published: February 2016

Three new hybrid ionic liquids (ILs) based on cage silsesquioxane (SQ) were rapidly prepared in high yields from octa(mercaptopropyl)silsesquioxane and 1‐allyl‐3‐methylimidazolium salts (Br−, BF4−, PF6−) through the photochemical thiol–ene reaction. These SQ‐based ILs exhibited low glass transition temperatures and good thermal stability. The unique amphiphilic nature of these hybrid ILs cause them to self‐assemble into perfect vesicles with “yolk–shell” structures, in which cages formed the “yolk” due to their aggregation and outer anions formed the “shell”.
Pillar[5]arene‐Based Glycoclusters: Synthesis and Multivalent Binding to Pathogenic Bacterial Lectins
Authors: Buffet Kevin , Nierengarten Iwona , Galanos Nicolas , Gillon Emilie , Holler Michel , Imberty Anne , Matthews Susan E. , Vidal Sébastien , Vincent Stéphane P. , Nierengarten Jean‐François
Published: February 2016

Invited for the cover of this issue are the groups of A. Imberty (Grenoble), S. Matthews (East Anglia), S. Vidal (Lyon), S. P. Vincent (Namur) and J.‐F. Nierengarten (Strasbourg). The image depicts an artistic view of bacterial lectins attracted by glycoclusters constructed on a pillar[5]arene scaffold. Read the full text of the article at 10.1002/chem.201504921.
Fungal Selenium(VI) Accumulation and Biotransformation—Filamentous Fungi in Selenate Contaminated Aqueous Media Remediation
Authors: Urík Martin , Boriová Katarína , Bujdoš Marek , Matúš Peter
Published: February 2016

While selenium is an essential trace element, its excessive intake causes adverse effects to human health. Therefore, selenium control and removal from water and soil are crucial in limiting environmental and human health risk. Various microorganisms have recently been exploited for use in remediation processes, especially filamentous fungi, which are efficient metal(loid) bioaccumulators with unique metabolic pathway of metal(loid) transformation into volatile derivatives. This contribution investigates the filamentous fungus Aspergillus clavatus' efficient and environmentally friendly selenium(VI) bioaccumulation and volatilization in selenium contaminated substrates remediation. The static batch culture experiments investigated these phenomena with initial selenium(VI) concentrations up to 89 mg L−1. The biovolatilization and bioaccumulation efficiency was calculated from selenium concentration data determined by inductively coupled plasma optical emission spectrometry in biomass and culture medium after a 14‐day cultivation period. The maximum selenium bioaccumulation capacity was almost 2.3 mg g−1 dry fungal biomass, with significant 2.8 mg g−1 biovolatilization during the 14‐day fungal incubation. Although bioaccumulation dominates selenium removal in diluted solutions, biotransformation into non‐harmful volatile derivatives ensures efficient selenium removal from aqueous media with extreme selenium concentrations up to 89 mg L−1. In contrast to biosorption/bioaccumulation process, biovolatilization leaves no solid residues with high selenium loads, thus confirming biovolatilization is the most suitable biological method for selenium removal from contaminated waters and sediments. In addition, filamentous fungal biomass application is highly beneficial in treatment of selenium contaminated aqueous media.
Design and Synthesis of Highly Active Peroxisome Proliferator‐Activated Receptor (PPAR) β/δ Inverse Agonists with Prolonged Cellular Activity
Authors: Toth Philipp M. , Lieber Sonja , Scheer Frithjof M. , Schumann Tim , Schober Yvonne , Nockher Wolfgang A. , Adhikary Till , Müller‐Brüsselbach Sabine , Müller Rolf , Diederich Wibke E.
Published: February 2016

Based on 3‐(((4‐(hexylamino)‐2‐methoxyphenyl)amino)sulfonyl)‐2‐thiophenecarboxylic acid methyl ester (ST247, compound 2), a recently described peroxisome proliferator‐activated receptor (PPAR)β/δ‐selective inverse agonist, we designed and synthesized a series of structurally related ligands. The structural modifications presented herein ultimately resulted in a series of ligands that display increased cellular activity relative to 2. Moreover, with methyl 3‐(N‐(2‐(2‐ethoxyethoxy)‐4‐(hexylamino)phenyl)sulfamoyl)thiophene‐2‐carboxylate (PT‐S264, compound 9 u), biologically relevant plasma concentrations in mice were achieved. The compounds presented in this study will provide useful novel tools for future investigations addressing the role of PPARβ/δ in physiological and pathophysiological processes.
SERS Tags: The Next Promising Tool for Personalized Cancer Detection?
Authors: Fabris Laura
Published: February 2016

Surface‐enhanced Raman scattering (SERS) has been historically considered a tool for physical scientists. Recently, however, a new avenue has opened for the application of SERS in the medical field, mainly spurred by the implementation of SERS tags. SERS tags are employed for the indirect identification of target molecules, similarly to what fluorescent dyes do, but with several intrinsic advantages. They have proven very useful in in vivo, ex vivo, and in vitro identification of cancerous cells and tissues, with targeting selectivity that can be tuned to recognize individual markers. It has also been demonstrated for the first time that surgical outcomes may be improved via the use of SERS tags, leading to complete tumor resection. Herein, I will explain how SERS tags can aid in the identification of cancerous tissues at the single cell level and how they promise to render SERS a powerful tool for personalized cancer detection.
Comparative Investigation of the Ionicity of Aprotic and Protic Ionic Liquids in Molecular Solvents by using Conductometry and NMR Spectroscopy
Authors: Thawarkar Sachin , Khupse Nageshwar D. , Kumar Anil
Published: February 2016

Electrical conductivity (σ), viscosity (η), and self‐diffusion coefficient (D) measurements of binary mixtures of aprotic and protic imidazolium‐based ionic liquids with water, dimethyl sulfoxide, and ethylene glycol were measured from 293.15 to 323.15 K. The temperature dependence study reveals typical Arrhenius behavior. The ionicities of aprotic ionic liquids were observed to be higher than those of protic ionic liquids in these solvents. The aprotic ionic liquid, 1‐butyl‐3‐methylimidazolium tetrafluoroborate, [bmIm][BF4], displays 100 % ionicity in both water and ethylene glycol. The protic ionic liquids in both water and ethylene glycol are classed as good ionic candidates, whereas in DMSO they are classed as having a poor ionic nature. The solvation dynamics of the ionic species of the ionic liquids are illustrated on the basis of the 1H NMR chemical shifts of the ionic liquids. The self‐diffusion coefficients D of the cation and anion of [HmIm][CH3COO] in D2O and in [D6]DMSO are determined by using 1H nuclei with pulsed field gradient spin‐echo NMR spectroscopy.
Hydrophilic Domains Enhance Nanobubble Stability
Authors: Nishiyama Takashi , Takahashi Koji , Ikuta Tatsuya , Yamada Yutaka , Takata Yasuyuki
Published: February 2016

Highly stable nanoscale gas states at solid/liquid interfaces, referred to as nanobubbles, have been widely studied for over a decade. In this study, nanobubbles generated on a hydrophobic Teflon amorphous fluoroplastic thin film in the presence and absence of hydrophilic carbon domains are investigated by peak force quantitative nanomechanics. On the hydrophobic surface without hydrophilic domains, a small number of nanobubbles are generated and then rapidly decrease in size. On the hydrophobic surface with hydrophilic domains, the hydrophilic domains have a significant effect on the generation and stability of nanobubbles, with bubbles remaining on the surface for up to three days.
Structures of Trichloromethyl Thiocyanate, CCl3SCN, in Gaseous and Crystalline State
Authors: Berrueta Martínez Yanina , Rodríguez Pirani Lucas S. , Erben Mauricio F. , Boese Roland , Reuter Christian G. , Vishnevskiy Yury V. , Mitzel Norbert W. , Della Védova Carlos O.
Published: February 2016

Trichloromethyl thiocyanate, CCl3SCN, was structurally studied in both the gas and crystal phases by means of gas electron diffraction (GED) and single‐crystal X‐ray diffraction (XRD), respectively. Both experimental studies and quantum chemical calculations indicate a staggered orientation of the CCl3group relative to the SCN group. This conclusion is supported by the similarity of the C−SCN bond length to that of theanti‐structure of CH2ClSCN (Berrueta Martínez et al.Phys. Chem. Chem. Phys. 2015,17, 15805–15812).Bond lengths and angles are similar for gas and crystal CCl3SCN structures; however, the crystal structure presents different intermolecular interactions. These include halogen and chalcogen type interactions, the geometry of which was studied. Characteristic C‐Y⋅⋅⋅N angles (Y=Cl or S) close to 180° provide evidence for typical σ‐hole interactions along the halogen/chalcogen−carbon bond in N⋅⋅⋅Cl and N⋅⋅⋅S, intermolecular units.
Spectroscopic Evidence for Clusters of Like‐Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding
Authors: Knorr Anne , Stange Peter , Fumino Koichi , Weinhold Frank , Ludwig Ralf
Published: February 2016

The front cover artwork is provided by the group of Prof. Ralf Ludwig at the University of Rostock in collaboration with Prof. Frank Weinhold at the University of Wisconsin Madison. The image shows the cyclic tetramer of hydrogen bonded cations in ionic liquids. The like‐charge attraction is supported by strong cooperativity and weakly coordinating anions. Read the full text of the Review at 10.1002/cphc.201501134
Switchable Room‐Temperature Ferroelectric Behavior, Selective Sorption and Solvent‐Exchange Studies of [H3O][Co2(dat)(sdba)2]⋅H2sdba⋅5 H2O
Authors: Bhattacharya Saurav , Pal Somnath , Natarajan Srinivasan
Published: February 2016

A newly synthesized compound, [H3O][Co2(dat)(sdba)2]⋅H2sdba⋅5 H2O (I, dat=3,5‐diamino‐1,2,4‐triazole; H2sdba=4,4′‐sulfonyldibenzoic acid), has Co2“paddlewheel” units connected by sdba ligands to form one‐dimensional chains, which are connected by dat to form an anionic three‐dimensional structure with cds topology. The one‐dimensional channels in the structure contain water molecules, hydronium ions and H2sdba. The water molecules could be reversibly exchanged with D2O, CH3OH and C2H5OH molecules; these exchanges were performed in a single‐crystal‐to‐single‐crystal manner. Gas sorption studies on the dehydrated compound showed the selective adsorption of CO2over methane at 195 K. Nonlinear optical measurements indicated thatIexhibits a second harmonic generation signal that is approximately one‐third that of urea. Studies of polarization versus electric field demonstrated compound Ias a potential room‐temperature ferroelectric material with a saturation polarization of 0.23 μC cm−2and remnant polarization of 0.14 μC cm−2. The dehydrated compound exhibited a simple paraelectric behavior.
Dealing with Resistance in Initial Intake and Inquiry Calls to Mediation: The Power of “Willing”
Authors: Sikveland Rein , Stokoe Elizabeth
Published: February 2016

This article explores how to best deal with resistance during and beyond initial encounters with prospective mediation clients. The study is based on a large data set of intake calls to community and family mediation services in the United Kingdom. Using conversation analytic techniques, we studied instances where call takers invited prospective clients to make a first appointment. We found that questions or proposals addressing whether the caller would be willing to mediate generated stronger agreement from the caller than when other formats were used. We discuss how to best establish effective practice in order to develop better training for mediators.
Wnt Signaling Inhibition Deprives Small Intestinal Stem Cells of Clonogenic Capacity
Authors: Janeckova Lucie , Fafilek Bohumil , Krausova Michaela , Horazna Monika , Vojtechova Martina , Alberich‐Jorda Meritxell , Sloncova Eva , Galuskova Katerina , Sedlacek Radislav , Anderova Miroslava , Korinek Vladimir
Published: February 2016

The Wnt pathway plays a crucial role in self‐renewal and differentiation of cells in the adult gut. In the present study, we revealed the functional consequences of inhibition of canonical Wnt signaling in the intestinal epithelium. The study was based on generation of a novel transgenic mouse strain enabling inducible expression of an N‐terminally truncated variant of nuclear Wnt effector T cell factor 4 (TCF4). The TCF4 variant acting as a dominant negative (dn) version of wild‐type (wt) TCF4 protein decreased transcription of β‐catenin‐TCF4‐responsive genes. Interestingly, suppression of Wnt/β‐catenin signaling affected asymmetric division of intestinal stem cells (ISCs) rather than proliferation. ISCs expressing the transgene underwent several rounds of division but lost their clonogenic potential and migrated out of the crypt. Expression profiling of crypt cells revealed that besides ISC‐specific markers, the dnTCF4 production downregulated expression levels of epithelial genes produced in other crypt cells including markers of Paneth cells. Additionally, in Apc conditional knockout mice, dnTCF activation efficiently suppressed growth of Apc‐deficient tumors. In summary, the generated mouse strain represents a convenient tool to study cell‐autonomous inhibition of β‐catenin‐Tcf‐mediated transcription. genesis 54:101–114, 2016. © 2016 The Authors genesis Published by Wiley Periodicals, Inc.
Sub‐annual variability in historical water source use by Mediterranean riparian trees
Authors: Sargeant Christopher I. , Singer Michael Bliss
Published: February 2016

The seasonal availability of water within a tree's rooting zone may be an important determinant for individual tree growth and overall forest health, particularly in riparian corridors of Mediterranean climate zones that are vulnerable to water stress. Here, we present a new method that combines dendro‐isotopes and isotope modelling for determining how water source use varies over 10 consecutive growing seasons (2000–2010) for co‐occurring species Populus nigra and Fraxinus excelsior, along the Rhône River, south‐eastern France. We conducted highly resolved δ18O analysis of cellulose micro‐slices within tree‐rings and back‐calculated the δ18O signature of source water available at the time of growth using a biochemical fractionation model. We related these patterns to inferred seasonal hydrological partitioning through comparison with δ18O of waters from the vadose and phreatic zones, precipitation and streamflow. The shallowly rooted Fraxinus displayed greater sub‐annual source water variability, as well as greater isotopic enrichment, reflecting use of precipitation‐derived vadose moisture. Its earlywood was formed mainly from winter rainfall (δ18O depleted) whilst the latewood was composed from growing season precipitation (δ18O enriched). In Populus, the sub‐annual source water use was relatively depleted, suggesting use of hyporheic water and regional groundwater. From 2007, both species converged in their pattern of water source uptake which was attributed to a decline in phreatic water access for Populus. These results demonstrate that the seasonal variability in source water use can be identified retrospectively, a method which may prove important for anticipating the future consequences of climate‐driven changes to the hydrological cycle. © 2016 The Authors. Ecohydrology published by John Wiley & Sons, Ltd.
Extremely Low Temperature Crystallization in the A2M3O12 Family of Negative Thermal Expansion Materials
Authors: Young Lindsay , Alvarez Pablo Torrico , Liu Hongfei , Lind Cora
Published: February 2016

A2M3O12 materials (A = Al, Sc, Fe, In, Ga, Y; M = Mo, W) were synthesized using the non‐hydrolytic sol‐gel process. In contrast to previous studies, in which amorphous materials were recovered that required heating to 500–700 °C to induce crystallization, several compounds could be crystallized in a temperature range compatible with low temperature processing of devices and composites. Under certain reaction conditions, crystalline Sc2Mo3O12, Fe2Mo3O12, and In2Mo3O12 were obtained at temperatures as low as 230 °C. This may allow use of these materials for in‐situ composite formation, which could result in new practical applications.
Chemoenzymatic Synthesis of α‐­Cyano Epoxides by a Tandem‐­Knoevenagel–Epoxidation Reaction
Authors: Fengjuan Yang  , Zhang Xiaowen , Li Fengxi , Wang Zhi , Wang Lei
Published: February 2016

An efficient lipase‐mediated synthesis of α‐cyano epoxides through a tandem‐Knoevenagel–epoxidation reaction was explored for the first time. This method provides a green, mild, and convenient route for the synthesis of α‐cyano epoxides; moreover, the applicability of lipase in organic synthesis is further extended.