bluuebunny/crossref_metadata_2025 huggingface dataset:
Solvent‐Driven Conformational Exchange for Amide‐Linked Bichromophoric BODIPY Derivatives
Authors: Thakare Shrikant , Stachelek Patrycja , Mula Soumyaditya , More Ankush B. , Chattopadhyay Subrata , Ray Alok K. , Sekar Nagaiyan , Ziessel Raymond , Harriman Anthony
Published: August 2016

The fluorescence lifetime and quantum yield are seen to depend in an unexpected manner on the nature of the solvent for a pair of tripartite molecules composed of two identical boron dipyrromethene (BODIPY) residues attached to a 1,10‐phenanthroline core. A key feature of these molecular architectures concerns the presence of an amide linkage that connects the BODIPY dye to the heterocyclic platform. The secondary amide derivative is more sensitive to environmental change than is the corresponding tertiary amide. In general, increasing solvent polarity, as measured by the static dielectric constant, above a critical threshold tends to reduce fluorescence but certain hydrogen bond accepting solvents exhibit anomolous behaviour. Fluorescence quenching is believed to arise from light‐induced charge transfer between the two BODIPY dyes, but thermodynamic arguments alone do not explain the experimental findings. Molecular modelling is used to argue that the conformation changes in strongly polar media in such a way as to facilitate improved rates of light‐induced charge transfer. These solvent‐induced changes, however, differ remarkably for the two types of amide.
Synthesis of Pyrrolo[2,3‐d]pyrimidines by Copper‐Mediated Carbomagnesiations of N‐Sulfonyl Ynamides and Application to the Preparation of Rigidin A and a 7‐Azaserotonin Derivative
Authors: Nickel Johannes , Fernández Maitane , Klier Lydia , Knochel Paul
Published: August 2016

The treatment of readily available N‐alkynyl‐5‐iodo‐6‐sulfamido‐pyrimidines with iPrMgCl⋅LiCl followed by a transmetalation with CuCN⋅2 LiCl produces, after intramolecular carbocupration, metalated pyrrolo[2,3‐d]pyrimidines. Quenching of these pyrimidines with allylic halides or acid chlorides results in polyfunctional pyrrolo[2,3‐d]pyrimidines. Further reaction with ICl and a Negishi cross‐coupling, using PEPPSI‐iPr as the catalyst, furnishes fully substituted N‐heterocycles. A formal synthesis of the marine alkaloid rigidin A has been achieved as well as the preparation of a derivative of 7‐azaserotonine, related to the natural hormone serotonin.
Ruthenium Metal–Organic Frameworks with Different Defect Types: Influence on Porosity, Sorption, and Catalytic Properties
Authors: Zhang Wenhua , Kauer Max , Halbherr Olesia , Epp Konstantin , Guo Penghu , Gonzalez Miguel I. , Xiao Dianne J. , Wiktor Christian , LIabrés i Xamena Francesc X. , Wöll Christof , Wang Yuemin , Muhler Martin , Fischer Roland A.
Published: August 2016

By employing the mixed‐component, solid‐solution approach, various functionalized ditopic isophthalate (ip) defect‐generating linkers denoted 5‐X‐ipH2, where X=OH (1), H (2), NH2 (3), Br (4), were introduced into the mixed‐valent ruthenium analogue of [Cu3(btc)2]n (HKUST‐1, btc=benzene‐1,3,5‐tricarboxylate) to yield Ru‐DEMOFs (defect‐engineered metal–organic frameworks) of the general empirical formula [Ru3(btc)2−x(5‐X‐ip)xYy]n. Framework incorporation of 5‐X‐ip was confirmed by powder XRD, FTIR spectroscopy, ultrahigh‐vacuum IR spectroscopy, thermogravimetric analysis, 1H NMR spectroscopy, N2 sorption, and X‐ray absorption near edge structure. Interestingly, Ru‐DEMOF 1 c with 32 % framework incorporation of 5‐OH‐ip shows the highest BET surface area (≈1300 m2 g−1, N2 adsorption, 77 K) among all materials (including the parent framework [Ru3(btc)2Yy]n). The characterization data are consistent with two kinds of structural defects induced by framework incorporation of 5‐X‐ip: modified paddlewheel nodes featuring reduced ruthenium sites (Ruδ+, 0<δ<2, type A) and missing nodes leading to enhanced porosity (type B). Their relative abundances depend on the choice of the functional group X in the defect linkers. Defects A and B also appeared to play a key role in sorption of small molecules (i.e., CO2, CO, H2) and the catalytic properties of the materials (i.e., ethylene dimerization and the Paal–Knorr reaction).
Exploring the Slow Relaxation of the Magnetization in CoIII‐Decorated {DyIII2} Units
Authors: Funes Alejandro V. , Carrella Luca , Rentschler Eva , Alborés Pablo
Published: August 2016

We have prepared and structurally characterized a new member of the butterfly‐like {CoIII2DyIII2} single‐molecule magnets (SMMs) through further CoIII decoration, with the formula [CoIII4DyIII2(OH)2(teaH)2(tea)2(Piv)6] (teaH3=triethanolamine; Piv=trimethylacetate or pivalate). Direct current (DC) susceptibility and magnetization measurements were performed allowing the extraction of possible crystal‐field parameters. A simple electrostatic modeling shows reasonable agreement with experimental data. Alternating current (AC) susceptibility measurements under a zero DC field and under small applied fields were performed at different frequencies (i.e., 10–1500 Hz) and at low temperatures (i.e., 2–10 K). Multiple magnetization relaxation pathways are observed. Comparison with previously reported {CoIII2DyIII2} complex measurements allows an overall discussion about the origin of the dynamic behavior and its relationship with crystal‐field split ground multiplet sublevels.
Unraveling the Amine‐Induced Disproportionation Reaction of Perchlorinated Silanes—A DFT Study
Authors: Schweizer Julia I. , Meyer Lioba , Nadj Andor , Diefenbach Martin , Holthausen Max C.
Published: August 2016

A detailed quantum‐chemical study on the amine‐induced disproportionation reaction of perchlorinated silanes toneo‐Si5Cl12is reported. The key intermediate in the resulting mechanistic scenario is a dichlorosilylene amine adduct, which is in tune with recent experimental findings. Yet, at variance with the generally accepted notion of silicon‐chain growth by concerted silylene insertion into Si−Cl bonds of lower silanes, the formation ofneo‐Si5Cl12follows more complex pathways. The reactivity is dominated by the Lewis–base character of the dichlorosilylene amine adduct and characterized by three elementary steps that bear close resemblance to the key elementary steps identified earlier for the chloride‐induced disproportionation of Si2Cl6. NBO and QTAIM analyses of the key reactive species SiCl2⋅NMe3and SiCl3−provide a rationale for these striking similarities.
Rotaxane‐Like Structures Threaded through the Pores of Hollow Porous Nanocapusles
Authors: Dergunov Sergey A. , Ehterami Nasim , Pinkhassik Eugene
Published: August 2016

Nanocapsules with molecules threaded through the porous shells may lead to advanced cell‐mimicking functional devices. Herein, we show the feasibility of synthesizing such hybrid nanostructures by using vesicle‐templated polymer nanocapsules with controlled nanopores. Ship‐in‐a‐bottle assembly inside a nanocapsule created an internal unit. An external unit was then connected to an entrapped internal unit through pre‐attached linker threaded through a nanopore in the shell of the nanocapsule. Both internal and external units are larger than the pore size and cannot cross the shell, producing a rotaxane‐like structure. Successful synthesis was achieved with fairly short linkers (six and ten carbon atoms in a chain), creating an opportunity for facile synthesis of functional devices capable of cross‐shell communication.
Nitroxide Radical Spin Probes for Exploring Halogen‐Bonding Interactions in Solution
Authors: Gualandi Lorenzo , Mezzina Elisabetta , Franchi Paola , Lucarini Marco
Published: August 2016

The synthesis of 2,3,5,6‐tetrafluoro‐4‐iodobenzyl tert‐butyl nitroxide (2‐I) and its use as spin probe for the detection of halogen‐bond (XB) complexes by EPR is reported. Formation of a XB complex between 2‐I and several XB acceptors was evidenced by a significant change in the value of the benzylic hyperfine splitting upon complexation. Thermodynamic parameters for the formation of XB complex with quinuclidine were obtained by recording EPR spectra in the temperature range 203–294 K. In addition, competitive experiments allowed for the measurement of the equilibrium constant of the XB complex with a chloride anion. The proposed procedure constitutes the first direct EPR methodology providing a reliable determination of the strength of the XB bond in solution.
Biodistribution and evaluation of 131I‐labeled neuropilin‐binding peptide for targeted tumor imaging
Authors: Dong Ping , Cai Huawei , Chen Lihong , Li Yalun , Yuan Cen , Wu Xiaoai , Shen Guohua , Zhou Huijun , Zhang Wenjie , Li Lin
Published: August 2016

Neuropilin‐1 (NRP‐1) is overexpressed in several kinds of cancer cell and contributes to tumor aggressiveness. Recently, the arginine/lysine‐rich peptide with C‐terminal motifs (R/K)XX(R/K) indicated promising penetrating and transporting capability into NRP‐1 positive cancer cells. In the present study, we describe a 131I‐labeled C‐end rule motif peptide conjugate, Tyr–tLyp‐1, for NRP‐1 positive tumor targeting and imaging properties. Briefly, a truncated Lyp‐1 peptide was designed to expose its C‐end motif and conjugated to tyrosine for radiolabeling after structural modification. The peptide indicated specific binding to A549 cancer cells at 2 μM concentration, and its binding was dependent on NRP‐1 expression and could be inhibited by other NRP‐1‐binding peptides. In vivo imaging of 131I‐labeled Tyr–tLyp‐1peptide showed that a subcutaneous A549 xenograft tumor could be visualized using a SPECT/CT scanner. The tumor uptake of 131I‐Tyr–tLyp‐1 was 4.77 times higher than the uptake in muscles by SPECT/CT software quantification at 6 h post injection. Together, this study indicated that truncated Lyp‐1 peptide could specifically localize in NRP‐1 positive tumors and successfully mediate the 131I radionuclide diagnosis, indicating promising targeted imaging capability for NRP‐1 positive tumors. Copyright © 2016 John Wiley & Sons, Ltd.
Frailty as determined by a comprehensive geriatric assessment‐derived deficit‐accumulation index in older patients with cancer who receive chemotherapy
Authors: Cohen Harvey Jay , Smith David , Sun Can‐Lan , Tew William , Mohile Supriya G. , Owusu Cynthia , Klepin Heidi D. , Gross Cary P. , Lichtman Stuart M. , Gajra Ajeet , Filo Julie , Katheria Vani , Hurria Arti ,   for the Cancer and Aging Research Group
Published: August 2016

BACKGROUND

Frailty has been suggested as a construct for oncologists to consider in treating older cancer patients. Therefore, the authors assessed the potential of creating a deficit‐accumulation frailty index (DAFI) from a largely self‐administered comprehensive geriatric assessment (CGA).

METHODS

Five hundred patients aged ≥65 years underwent a CGA before receiving chemotherapy. A DAFI was constructed, resulting in a 51‐item scale, and cutoff values were examined for patients in the robust/nonfrail (cutoff value, 0.0 < 0.2), prefrail (cutoff value, 0.2 < 0.35), and frail (cutoff value, ≥ 0.35) groups.

RESULTS

Two hundred and fifty patients (50%) were nonfrail, 197 (39%) were prefrail, and 52 (11%) were frail. Older patients (aged ≥ 80 years) and those who had lower education, were living alone, and had higher stage disease were associated with prefrail/frail status. Prefrail/frail patients were more likely to have grade ≥3 toxicity but not to have a dose delay or reduction, and they were more likely to discontinue drug and be hospitalized. The association with grade ≥3 toxicity was attenuated by controlling for a toxicity risk calculator, but the other outcomes were not.

CONCLUSIONS

A deficit‐accumulation frailty index can be constructed from a CGA in older patients with cancer and can indicate the frailty status of the population. The frailty status so determined is associated both with outcomes likely because of chemotherapy toxicity and with those likely because of age‐related physiologic and functional deficits and thus can be useful in the overall assessment of the patient. Cancer 2016;122:3865–3872. © 2016 American Cancer Society.
Algorithmic approach to neuroendocrine tumors in targeted biopsies: Practical applications of immunohistochemical markers
Authors: Duan Kai , Mete Ozgur
Published: August 2016

Neuroendocrine tumors (NETs) constitute a heterogeneous group of neoplasms with distinct biological behaviors, depending on the site of origin and the degree of tumor proliferation. Although advances in biochemical and radiological modalities have enhanced the ability to detect NETs, tissue diagnosis remains the gold standard to assess tumor characteristics for treatment decision making. In an era with growing demands for precision diagnostics based on smaller tissue samples, immunohistochemistry has become an indispensable tool in the pathologist's repertoire. In conjunction with clinical findings and cytomorphology, complementary use of 1) markers of neuroendocrine differentiation, 2) markers confirming epithelial nature, 3) markers of cellular proliferation, 4) transcription factors and hormonal markers, as well as 5) predictive and prognostic markers may be necessary to guide patient management in NETs. The current review summarizes common applications of these immunohistochemical markers when confronted with a potential neuroendocrine neoplasm, and proposes a stepwise algorithmic approach to avoid diagnostic errors in targeted biopsies. Cancer Cytopathol 2016;124:871–884. © 2016 American Cancer Society.
A ZnO/TiO2 composite nanorods photoanode with improved performance for dye‐sensitized solar cells
Authors: Feng Yamin , Chen Jinghua , Huang Xintang , Liu Weifeng , Zhu Yu , Qin Wei , Mo Xiaoyuan
Published: August 2016

A dye‐sensitized solar cell (DSSC) based on ZnO/TiO2 composite nanorods (NRs) photoanode is fabricated. The power conversion efficiency (PCE) of the ZnO/TiO2 composite NRs film DSSC is 4.36%, which is obviously higher than that of DSSCs based on pure TiO2 NRs (0.6%) and ZnO NRs (3.10%). The enhanced performance of ZnO/TiO2 composite NRs film DSSC can be attributed to the combined effects of ZnO and TiO2 NRs. In this architecture, the thick ZnO NRs overlayer offers a large surface area for enough dye absorption, while the thin TiO2 NRs underlayer not only offers a direct and quick pathway for photoinjected electron transfer along the photoanode but also acts as a blocking layer, which effectively hinders the direct contact between the substrate and the electrolyte resulting in lower carrier recombination.
Ordered Mesoporous Polymers for Biomass Conversions and Cross‐Coupling Reactions
Authors: Liu Fujian , Wu Qin , Liu Chen , Qi Chenze , Huang Kuan , Zheng Anmin , Dai Sheng
Published: August 2016

Amino group‐functionalized, ordered mesoporous polymers (OMP‐NH2) were prepared using a solvent‐free synthesis by grinding mixtures of solid raw precursors (aminophenol, terephthaldehyde), using block copolymer templates, and curing at 140–180 °C. OMP‐NH2 was functionalized with acidic sites and incorporated with palladium, giving multifunctional solid catalysts with large Brunauer–Emmett–Teller (BET) surface areas, abundant and ordered mesopores, good thermal stabilities, controllable concentrations, and good dispersion of active centers. The resultant solid catalysts showed excellent catalytic activities and good reusability in biomass conversions and cross‐coupling reactions—much superior to those of various reported solid catalysts such as Amberlyst 15, SBA‐15‐SO3H, and Pd/C and comparable to those of homogeneous catalysts such as heteropoly acid, HCl, and palladium acetate. A facile green approach was developed for the synthesis of ordered mesoporous polymeric solid catalysts with excellent activities for conversion of low‐cost feedstocks into useful chemicals and clean biofuels.
New approach for spacing of movement joints in reinforced and unreinforced masonry veneer walls. Part 1: Unreinforced masonry / Neue Bemessungsmethode für die Abstände von Dehnungsfugen in bewehrten und unbewehrten Verblendmauerwerksschalen. Teil 1: Unbewehrtes Mauerwerk
Authors: Martens Dirk R.W.
Published: August 2016

The spacing of movement joints has been subject of many discussions. The current methods for the determination of the spacing of movement joints are based on local traditions and bad experience with cracked veneer walls. This has resulted in various design rules throughout Europe with very stringent limits for spacing of movement joints. According to EC6, one of the solutions for increasing the spacing of movement joints is to introduce bed joint reinforcement, although unfortunately no specific design rules are given. Until now, most scientific research has been focused on numerical simulations without taking time‐dependent effects into account, which is a conservative approach. In this paper, a new approach is described. It is based on Peter Schubert's model and on practical experience with masonry buildings.
Bond behaviour between textile reinforcement and mortar under tensile loading / Verbundverhalten zwischen textiler Bewehrung und Mörtel unter Zugbeanspruchung
Authors: Saenger Dorothea , Brameshuber Wolfgang
Published: August 2016

Extensive experimental investigations are currently being carried out on various selected materials covering a wide range of properties to achieve a deeper knowledge about the bond performance of textile reinforced mortar (TRM) for masonry strengthening. The objective of the tests includes investigations of the bonding behaviour between alkali‐resistant glass textile reinforcement and mortar under tensile loading to determine the required anchorage and overlapping lengths of the reinforcement in the mortar‐based material. This article describes the test methods used as well as the results obtained so far. This research will also examine debonding of the mortar‐based reinforcement system and the masonry surface under shear load. The definition of these bond parameters is necessary for the design of textile‐reinforced masonry components, which will be developed in the near future. The research is also intended to contribute to the finding or even designing of matching alkali‐resistant glass textiles specifically for use in masonry.
Bracing systems in masonry buildings. Part 1: Simple application of FE programs / Aussteifungssysteme im Mauerwerksbau. Teil 1: Einfache Anwendung von FE‐Programmen
Authors: Sommerlade Kai , Seim Werner
Published: August 2016

Due to the low tensile strength of masonry perpendicular to the bed joint, masonry wall panels have non‐linear material properties. Assuming simple elastic constitutive laws, this article presents two modelling variants, which consider the lack of tensile strength in a simple manner. Both variants are investigated for their advantages and disadvantages. In a second part of the article, the application of the methods will be illustrated through the example of a four‐storey building.
Risk of HSIL (CIN 2–3) on colposcopic biopsy is minimal in postmenopausal women with LSIL on cytology and a negative HRHPV test
Authors: Ozturk Mustafa , Umudum Haldun , Alanbay Ibrahim , Ulubay Mustafa , Fidan Ulas , Dede Murat , Yenen Müfit Cemal
Published: August 2016

Background

Current cervical cancer screening guidelines recommend a 1‐year follow‐up period for patients with a postmenopausal low‐grade squamous intraepithelial lesion (LSIL) who are test negative for high‐risk human papillomavirus (HrHPV). The aim of this study was to assess whether such patients had an increased immediate risk of high‐grade squamous intraepithelial lesion.

Methods

We assessed 54 HrHPV‐negative women with postmenopausal LSIL in the Department of Obstetrics and Gynecology of our hospital between 2012 and 2013. All patients underwent liquid‐based cytology and reflex HrHPV testing (for human papillomavirus [HPV] types 16, 18, 31, 33, 35, 39, 45, 51, 52, 56, 58, 59, 66, and 68). Colposcopic examination and guided biopsy were performed by the same gynecologist (MO).

Results

The average age of the patients was 53.1 ± 3.2 years. There were 33 patients (61%) with cervical intraepithelial neoplasia (CIN) grade 1 and 21 who were non‐dysplastic. None of the patients was positive for CIN 2 or any other lesions.

Conclusions

If the HPV test is negative, repeat cytology after 12 months is recommended by the American Society for Colposcopy and Cervical Pathology for cases of HrHPV‐negative postmenopausal LSIL. We recommend reflex HPV testing as the best choice for patients who test positive for postmenopausal LSIL by Pap smear, in line with the literature. Diagn. Cytopathol. 2016;44:969–974. © 2016 Wiley Periodicals, Inc.
Childhood pulmonary langerhans cell histiocytosis in bronchoalveolar lavage: A case report along with review of literature
Authors: Sharma Sudha , Dey Pranab
Published: August 2016

Isolated pulmonary Langerhans cell histiocytosis (LCH) is rare in childhood, and few cases have been diagnosed on bronchoalveolar lavage (BAL) smears. We hereby report a child with cystic lesions in both lungs diagnosed as LCH on BAL smears and compare the cytomorphologic findings with BAL smears of five patients with various pathologies. The BAL smears of the index case showed numerous macrophages with many atypical histiocytes showing coffee bean‐shaped nuclei, nuclear grooving along with few giant cells. Immunocytochemistry for S‐100 protein and CD1a was positive in these cells (16.5%). The mean percentage of macrophages showing nuclear grooving, bi‐nucleation, and multinucleation was much higher in the case with LCH compared to the other cases. Review of literature and the present case study shows that in the presence of appropriate radiologic findings, characteristic morphologic features and demonstration of 5% or more CD1a positive cells in BAL is strongly suggestive of pulmonary LCH. Diagn. Cytopathol. 2016;44:1102–1106. © 2016 Wiley Periodicals, Inc.
Transitioning from DSM‐IV to DSM‐5: A systematic review of eating disorder prevalence assessment
Authors: Lindvall Dahlgren Camilla , Wisting Line
Published: August 2016

Objective

The objective of this study was to systematically review the literature on assessment of eating disorder prevalence during the DSM‐IV era (1994–2015).

Method

A PubMed search was conducted targeting articles on prevalence, incidence and epidemiology of eating disorders. The review was performed in accordance with PRISMA guidelines, and was limited to DSM‐IV based eating disorder diagnoses published between 1994 and 2015.

Results

A total of 74 studies fulfilled inclusion criteria and were included in the study. Results yielded evidence of over 40 different assessment instruments used to assess eating disorder prevalence, with the EAT‐40 being the most commonly used screening instrument, and the SCID being the most frequently used interview. The vast majority of studies employed two‐stage designs, closely followed by clinical interviews. Observations of higher prevalence rates were found in studies employing self‐reports compared to two‐stage designs and interviews.

Discussion

Eating disorder prevalence rates have varied significantly during the DSM‐IV era, and are dependent on assessment methods used and samples investigated. Following the transition to the DSM‐5, eating disorder prevalence will change, warranting novel approaches to assessment and treatment planning. © 2016 Wiley Periodicals, Inc.
Examination of parental dieting and comments as risk factors for increased drive for thinness in men and women at 20‐year follow‐up
Authors: Klein Kelly M. , Brown Tiffany A. , Kennedy Grace A. , Keel Pamela K.
Published: August 2016

Objective

Popular beliefs suggest that parents influence children's eating disorder risk through modeling pathological behaviors and attitudes, and this history may contribute to disordered eating in adulthood. However, the empirical basis for this popular thinking is limited by a reliance on cross‐sectional designs that do not distinguish between maternal and paternal influences and use primarily child and adolescent samples. To address these limitations, the present study examined the impact of maternal and paternal dieting and comments about weight and eating, as reported by late adolescents, on the eating pathology of those late adolescents at 20‐year follow‐up.

Method

Data were drawn from a longitudinal epidemiological study of health and eating patterns in a cohort of randomly sampled college students established in 1992 (N = 799; mean age: 19.87 [±1.64] years; 70.8% women) and followed 20 years later in 2012 (N = 539).

Results

At baseline, there were no gender differences in reported rates of maternal or paternal dieting. Both men and women reported higher levels of maternal versus paternal dieting. Further, women endorsed higher levels of maternal and paternal comments on their own weight and eating. A multivariable model in women supported that maternal dieting and paternal comments significantly predicted drive for thinness at follow‐up. No parental variables predicted drive for thinness in men at follow‐up.

Discussion

While our study supports parental influence on children's eating attitudes, it suggests a need to consider gender and mode of influence. Prevention efforts focused on challenging cultural standards of appearance may benefit from incorporation of parents. © 2016 Wiley Periodicals, Inc.(Int J Eat Disord 2017; 50:490–497)
Bone density, body composition, and psychopathology of anorexia nervosa spectrum disorders in DSM‐IV vs DSM‐5
Authors: Schorr Melanie , Thomas Jennifer J. , Eddy Kamryn T. , Dichtel Laura E. , Lawson Elizabeth A. , Meenaghan Erinne , Lederfine Paskal Margaret , Fazeli Pouneh K. , Faje Alexander T. , Misra Madhusmita , Klibanski Anne , Miller Karen K.
Published: August 2016

Objective

DSM‐5 revised the diagnostic criteria for anorexia nervosa (AN) by eliminating the amenorrhea requirement, liberalizing weight and psychological criteria, and adding the formal diagnosis of “atypical AN” for individuals with AN psychological symptoms without low weight. We sought to determine whether bone density (BMD) is impaired in women diagnosed with AN using the new, more liberal, DSM‐5 criteria.

Method

Cross‐sectional study of 168 women, 18 − 45y: (1) AN by DSM‐IV (DSM‐IV AN) (n = 37), (2) AN by DSM‐5 but not DSM‐IV criteria (DSM‐5 AN) (n = 33), (3) atypical AN (ATYPICAL AN) (n = 77), (4) healthy comparison group (HC) (n = 21). Measurements included dual energy X‐ray absorptiometry, Eating Disorder Examination‐Questionnaire, Eating Disorder Inventory‐2, Hamilton Depression and Anxiety Rating Scales.

Results

BMD Z‐score <−1.0 was present in 78% of DSM‐IV, 82% of DSM‐5, and 69% of ATYPICAL. Mean Z‐scores were comparably low in DSM‐IV and DSM‐5, intermediate in ATYPICAL, and highest in HC. Lack of prior low weight or amenorrhea was, but history of overweight/obesity was not, protective against bone loss. Mean lean mass and percent fat mass were significantly lower in all AN groups than HC. DSM‐IV, DSM‐5, and ATYPICAL had comparable psychopathology.

Discussion

Despite liberalizing diagnostic criteria, many women diagnosed with AN and atypical AN using DSM‐5 criteria have low BMD. Presence or history of low weight and/or amenorrhea remain important indications for DXA. Loss of lean mass, in addition to fat mass, is present in all AN groups, and may contribute to low BMD. The deleterious effect of eating disorders on BMD extends beyond those with current low weight and amenorrhea. © 2016 Wiley Periodicals, Inc.(Int J Eat Disord 2017; 50:343–351)
Amidinium‐Containing 2D [MnCr] Dimetallic Oxalate‐Based Networks – The Influence on Structure and Magnetism Explored by Combining Experience and Theory
Authors: Maxim Catalin , Saureu Sergi , de Graaf Coen , Ferlay Sylvie , Hosseini Mir Wais , Robert Vincent , Train Cyrille
Published: August 2016

Three X2+ bisamidinium dications are inserted into oxalate‐based dimetallic [MnCr] compounds of formula X[MnII(CH3OH)CrIII(ox)3]2·nS [X2+ = C14N4H202+ (cation A2+, compound 1), C14O2N4H202+ (cation B2+, compound 2), C16N4H242+ (cation C2+, compound 3); n = 4 (1–2), 2 (3); S = CH3OH (1–2), CH3CN (3); ox = oxalate]. Single‐crystal X‐ray analysis of 1–3 reveals that Mn–Cr oxalate‐bridged dimetallic coordination networks form corrugated two‐dimensional (2D) layers based on heptacoordinate MnII ions surrounded by six oxygen atoms from three bis‐bidentate oxalate ions and one oxygen atom from a coordinated methanol molecule. In 1–3, the observed coordination environments of the MnII ions are close to capped trigonal prismatic (CTPR‐7) according to continuous shape measurements (CSM). Curie–Weiss temperatures of 0.62, 0.42, and 0.54 K for 1–3, respectively, were deduced from the magnetic susceptibility measurements and reveal dominant ferromagnetic exchange interactions. Ab initio calculations up to the DDCI‐2 level were performed on [MnCr] dimeric units and allowed the evaluation of the exchange interactions in 1–3.
Evaluation of Perylene Bisimide‐Based RuII and IrIII Complexes as Photosensitizers for Photodynamic Therapy
Authors: Mari Cristina , Huang Huaiyi , Rubbiani Riccardo , Schulze Marcus , Würthner Frank , Chao Hui , Gasser Gilles
Published: August 2016

The synergistic action of a photosensitizer (PS), light, and oxygen is exploited in photodynamic therapy (PDT) to kill cancer cells with reduced side‐effects compared with traditional chemotherapeutic treatments. In this regard, new PSs are still necessary to improve the efficacy and the outcomes of this medical technique. Over the past years, metal complexes have attracted interest as alternatives to traditional porphyrin and phthalocyanin‐based PSs because of their tunable and thus tailor‐made photophysical properties. Among others, RuII and IrIII derivatives have shown promising results. Here, we report on the investigation of [Ru(bpy)2(ab‐PBI)][PF6]2 (1) and [Cp*Ir(ab‐PBI)Cl]PF6 (2), where bpy = 2,2′‐bipyridine, ab‐PBI = azabenz‐annulated perylene bisimide, and Cp* = pentamethylcyclopentadiene, as potential PDT PSs. These compounds display good photostability, as well as interesting singlet oxygen generation upon irradiation at 420 nm (in particular 2). Their biological activity was evaluated on four cell lines and, although the cytotoxicity of 1 did not improve significantly upon light irradiation, 2, which localizes in mitochondria of HeLa cells as indicated by ICP‐MS measurements, reached nanomolar IC50 values on all the cell lines tested when activated with 420 nm light in low doses (9.27 J cm–2).
3,5‐Dimethylpyrazolyl‐Substituted Di‐ and Trisiloxanes
Authors: Bitto Florian , Brendler Erica , Böhme Uwe , Wagler Jörg , Kroke Edwin
Published: August 2016

The synthesis and characterization of di‐ and trisiloxanes with 3,5‐dimethylpyrazolyl (pz*) moieties are presented. Disiloxanes of the type O(SiMe3–npz*n)2 (n = 1, 2, and 3 in 2, 3, and 4, respectively) are easily accessible through a trans‐silylation approach. Crystal structure analyses of compound 4 and the two side products 5 and 6 illustrate different coordination motifs of pz* (terminal vs. bridging) in the disiloxane system. The reaction of O2Si3Cl8 with Me3Sipz* led to the unsymmetrically substituted trisiloxane pz*3SiO‐Sipz*2O‐SiCl2pz* (7) with bridging pz* units and tetra‐ and pentacoordinate silicon atoms and the fully pyrazolyl‐substituted trisiloxane O2Si3pz*8 (8), depending on the choice of the reaction conditions. The 29Si NMR properties of 7 were investigated by 29Si CP/MAS NMR spectroscopy and supporting quantum chemical calculations analyzing the principal components of the chemical‐shift tensor for all three silicon atoms in this molecule.
A {Cu4I4} Cluster Supported on a Metal‐Dithiolato Complex Anion Causes its Conformational Change Leading to a Doubly‐Bridged Curved Coordination Polymer and its Reactivity with a Diamine Resulting in the Emergence of a [M(diamine)(dithiolate)] System
Authors: Madhu Vedichi , Bolligarla Ramababu , Naik Indravath K. , Mekala Raju , Das Samar K.
Published: August 2016

When dithiolene‐based coordination complexes [Bu4N]2[MII(tdas)2] (tdas2– = 1,2,5‐thiadiazole‐3,4‐dithiolate; M = Ni, Pd, Pt) are reacted separately with CuI, it results in the formation of chain‐like coordination polymers [Bu4N]2n[MII(tdas)2Cu4I4]n [M = Ni (compound 1), Pd (compound 2), Pt (compound 3)] in which each metal(bis)dithiolato complex unit supports a {CuI4I4} cluster unit. Two of the crystal structures and powder X‐ray diffraction studies confirm that compounds 1, 2 and 3 are isomorphous with each other showing the abundance of a doubly‐bridged “curved” chain‐like structure formed by the coordination of two “N” donor atoms of each [MII(tdas)2]2– complex unit to two Cu+ ions of two adjacent {CuI4I4} cluster units and by the coordination of two Cu+ ions of a {CuI4I4} cluster with its neighbouring two [MII(tdas)2]2– complex anions through their “N” donor atoms from opposite sides. Since the [MII(tdas)2]2– complex anion generally has a planar geometry, which becomes bent upon supporting a {CuI4I4} cluster in the present study, the Cu–S interaction in [MII(tdas)2Cu4I4]2– is responsible for the bending conformation of the metal–dithiolato complex unit. This bending structure of the complex anion [MII(tdas)2]2– in [MII(tdas)2Cu4I4]2– describes a situation where the central part of the complex anion is pulled away towards the {CuI4I4} cluster through Cu–S bonds. This causes a “curve‐like” structure throughout the resulting doubly‐bridged chain in compounds 1, 2 and 3. The second important aspect of the present work is an interesting reactivity of this doubly‐bridged coordination polymer with a bidentate chelating ligand, tetramethylethylenediamine (TMEDA). Compound [Bu4N]2n[NiII(tdas)2Cu4I4]n (1), a representative member of the series of compounds 1–3, was treated with TMEDA, which resulted in a square planar complex [Ni(tdas)(TMEDA)] (4) belonging to a mononuclear [MII(N2S2)]‐type system (where N2 = bidentate N∩N donor ligand, mostly a bipyridine type, and S2 = dithiolato ligand) representing an important class of compounds for photophysical properties. Compound 4 exhibits emission at room temperature in the visible region.
Neutral and Cationic Palladium Complexes of P‐Stereogenic Phosphanes Bearing a Heterocyclic Substituent
Authors: Clavero Pau , Grabulosa Arnald , Rocamora Mercè , Muller Guillermo , Font‐Bardia Mercè
Published: August 2016

The coordination chemistry of 13 optically pure P‐stereogenic diarylmonophosphanes P(Het)PhR [Het = 4‐dibenzofuranyl (DBF), 4‐dibenzothiophenyl (DBT), 4‐dibenzothiophenyl S,S‐dioxide (DBTO2) and 1‐thianthrenyl (TA); R = OMe, Me, iPr, Fc (ferrocenyl)] to Pd‐allyl moieties is described. Both neutral [PdCl(η3‐(2‐methylallyl)(κP‐P)] and cationic [Pd{η3‐(2‐methylallyl)(κP‐P)2}]PF6 complexes have been prepared. Coordination of the heteroatom of the heterocycle was only possible in the case of TA‐based phosphanes; these furnished complexes of the type [Pd{η3‐(2‐methylallyl)(κ2P,S‐P)}]PF6 after chloride abstraction with TlPF6. The crystal structure of the complex [Pd(η3‐2‐methylallyl)(κ2P,S‐PPh(OMe)(1‐TA)]PF6 is reported. The neutral Pd complexes were found to be highly active in the hydrovinylation of styrene after activation with AgBF4, except for the TA‐based phosphanes. The cationic Pd complexes were evaluated in allylic alkylation and amination with the model substrate rac‐trans‐1,3‐diphenylprop‐2‐enyl acetate (rac‐I), achieving total conversions and up to 70 % ee.
The Role of Bulkiness in Haptotropic Shifts of Metal–Cumulene Complexes
Authors: Huidobro‐Meezs Isaac L. , Segovia‐Poncelis Midori , Barquera‐Lozada José Enrique
Published: August 2016

In metal–cumulene complexes, the metal easily slides through the double bonds of the chain. A series of late‐transition‐metal–[5]cumulene complexes has been studied by theoretical and experimental methods in order to understand the factors that control such haptotropic shifts. The bulkiness of the cumulene terminal groups plays a central role in the tautomeric preferences. The quantum theory of atoms in molecules and the electron localizability indicator show that the M–C bond closer to the terminal groups is significantly weakened by steric interactions between these groups and the rest of ligands around the metal center. The results emphasize that special attention should be paid to the orientation of both the bulky substituents at the cumulene and other voluminous ligands around the metal, because the orientation of such moieties is important in predicting the direction of the haptotropic equilibrium correctly.
Snap‐Shots of a Reduction Pathway: The Reaction of WCl6 with Copper Powder
Authors: Mos‐Hummel Agnieszka , Ströbele Markus , Meyer Hans‐Jürgen
Published: August 2016

A combined differential scanning calorimetry (DSC)/X‐ray diffraction (XRD) methodology is used to search and identify compounds in the Cu/W/Cl system based on the successive reaction of WCl6 with copper powder. Thermal effects monitored by DSC are used to detect reaction pathways and phase formations of compounds. A series of five new and one already known compounds is discovered as crystalline phases in the Cu/W/Cl system and structurally characterized by XRD. The reaction of WCl6 with elemental copper begins at temperatures as low as 60 °C with the formation of crystalline powders of α‐CuxWCl6. Continuing reaction stages include the successive formation of crystalline phases β‐CuxWCl6, γ‐CuxWCl6, α‐Cu2W2Cl10, β‐Cu2W2Cl10, and Cu2[W6Cl14].
Synthesis and Conformational Study of Monosubstituted Aminoferrocene‐Based Peptides Bearing Homo‐ and Heterochiral Pro‐Ala Sequences
Authors: Čakić Semenčić Mojca , Kodrin Ivan , Barišić Lidija , Nuskol Marko , Meden Anton
Published: August 2016

The synthesis and conformational analysis of a series of the monosubstituted aminoferrocene‐based peptides bearing homo‐ and heterochiral Pro‐Ala sequences are described. A change of the Pro amino acid chirality can affect the secondary structure. The homochiral derivatives of tBuCO–AA2–AA1–NHFc (Fc = ferrocene; AA = Pro, Ala) favour β‐turns, and a disruption of the secondary structure is observed for the heterochiral analogues in solution. A detailed computational study suggested that γ‐turns form in the heterochiral derivatives. The X‐ray‐determined crystal structures of the heterochiral compounds show a preference for β‐turns. The calculated interaction energies indicate the significance of the intermolecular hydrogen bonds, which are favourable enough to overcome the rearrangement of a single molecule from the most stable conformer to that adopted in the solid state. The current research indicates the potential of the investigated compounds for the fine tuning of their conformational properties by variation of the chirality of the constituent amino acids.
Reactions of the Lithiated Diphosphine tBu2P–P(SiMe3)Li with [(η6‐C6H6)RuCl2]2 in the Presence of Tertiary Phosphines
Authors: Ponikiewski Łukasz , Kruczyński Tomasz , Caporali Maria , Peruzzini Maurizio , Gudat Dietrich , Walaszkowska Marta , Pikies Jerzy
Published: August 2016

tBu2P–P(SiMe3)Li reacted with [(η6‐C6H6)RuCl2]2 at –40 °C in the presence of PR3 (PR3 = PEt3, PEt2Ph, PEtPh2) by the nucleophilic addition of the tBu2P–P(SiMe3) moiety to the benzene ring to yield solely the complexes [(R3P)2Ru(Cl){η5‐C6H6(Me3SiP–PtBu2)}] (1). These products decomposed slowly at ambient temperature to yield benzene, Ru clusters, and small amounts of the dinuclear ruthenium complexes [{(R3P)2Ru}2(µ,η2:2‐P2)2Ru(PR3)2] (Ru–Ru) (6). Single‐crystal X‐ray diffraction studies of [(PhEt2P)2Ru(Cl){η5‐C6H6(Me3SiP–PtBu2)}] (1b) and [(Ph2EtP)2Ru(Cl){η5‐C6H6(Me3SiP–PtBu2)}] (1c) revealed that the addition of the tBu2P–P(SiMe3) group occurred through an exo pathway. Complex 6a (R = Et) displays a planar rectangular P4 system consisting of two P2 units and a Ru–Ru distance that lies in the range of a single bond.
σ‐Bond Activation in Aluminium‐Functionalized Alkynylchlorogermanes: Facile Insertion of Isocyanate and Azide into Al–C and Ge–Cl Bonds
Authors: Uhl Werner , Honacker Christian , Hepp Alexander , Layh Marcus , Würthwein Ernst‐Ulrich
Published: August 2016

Hydroalumination of Cl‐functionalized alkynylgermanes yielded mixed Al/Ge compounds (1). The Cl atoms adopted bridging positions between the Ge and Al atoms to form four‐membered GeCAlCl heterocycles with relatively long endocyclic Ge–Cl and Al–C bonds. Reactions with isocyanates resulted in the insertion of the heterocumulenes into both activated bonds and the formation of four‐membered GeC2N heterocycles, which featured exocyclic C–C and C–O double bonds with C–O oxygen atoms coordinated to ClAltBu2 molcules (2). An intermediate (3) was isolated with Ad‐NCO (Ad = 1‐adamantyl) from the insertion of isocyanate into the endocyclic Al–C bond. These products are characterized by intact Ge–Cl bonds and a chelating coordination of the Al atoms by the OCN groups. They rearranged at elevated temperature to yield compounds of type 2. Quantum‐chemical calculations were applied to evaluate the thermodynamics of these isocyanate insertion reactions. An azide reacted similarly by insertion into the Al–C and Ge–Cl bonds and afforded a GeCN3 heterocycle with an intact N3 group.
The Interaction of 1,1′‐Diphosphaferrocenes with Gold: Molecular Coordination Chemistry and Adsorption on Solid Substrates
Authors: Liebscher Michél , Bruhn Clemens , Siemeling Ulrich , Baio Joe , Lu Hao , Weidner Tobias
Published: August 2016

1,1′‐Diphosphaferrocene (1) and its 3,3′,4,4′‐tetramethyl (2), 3,3′,4,4′‐tetraphenyl (3), octamethyl (4), octaethyl (5) and octaphenyl derivative (6) have been investigated in terms of the suitability of 1,1′‐diphosphaferrocenes as adsorbate species for fabricating self‐assembled monolayers (SAMs) on gold. Compounds 3 and 6 have been structurally characterised by X‐ray diffraction. Complexes [Au(4)2][GaCl4] and [Au2(µ‐5)2][FeCl4]2 have also been prepared and are only the second and third examples to date of structurally characterised (1,1′‐diphosphaferrocene)gold complexes. [Au(4)2][GaCl4] exhibits intramolecular Au···Fe contacts compatible with Fe→Au bonding interactions, which have not been described before in ferrocene chemistry. [Au2(µ‐5)2][FeCl4]2 exhibits an intramolecular Au···Au contact indicative of aurophilic bonding, leading to a structural motif unprecedented for 1,1′‐diphosphaferrocenes. Ultrathin films obtained by chemisorption of the 1,1′‐diphosphaferrocenes from solution onto gold substrates have been investigated by X‐ray photoelectron spectroscopy and near‐edge X‐ray absorption fine‐structure (NEXAFS) spectroscopy. The results indicate that the surface binding of 1 involves the Fe atom together with both P atoms, whereas in the other cases, surface binding can be realised with just one phospholyl ring. There is no indication of any oxidative decomposition of the adsorbates on the surface. According to NEXAFS spectroscopic results 6 gives rise to SAMs of high orientational order.
Hand in Hand: Experimental and Theoretical Investigations into the Reactions of Copper(I) Mono‐ and Bis(guanidine) Complexes with Dioxygen
Authors: Hoffmann Alexander , Wern Miriam , Hoppe Tobias , Witte Matthias , Haase Roxana , Liebhäuser Patricia , Glatthaar Jörg , Herres‐Pawlis Sonja , Schindler Siegfried
Published: August 2016

Mono‐ and bis(guanidine) ligands stabilise bis‐µ‐oxido dicopper(III) complexes. Here, the formation of these complexes has been investigated in detail by means of low‐temperature stopped‐flow techniques for the monoguanidine 2‐[3‐(dimethylamino)propyl]‐1,1,3,3‐tetramethylguanidine (TMGdmap) and the related bis(guanidine) 1,3‐bis(N,N,N′,N′‐tetramethylguanidino)propane (btmgp). Low‐temperature IR studies in solution support the formation of bis‐µ‐oxido complexes. For both systems, no intermediates on the pathways to the bis‐µ‐oxido complexes could be detected; this has been explained through extensive DFT calculations. In the first step, the oxygen reduction during the binding to the copper(I) complex to form a superoxido species was studied. In the second step, the full path from superoxido through trans‐µ‐peroxido to side‐on peroxido and finally bis‐µ‐oxido was modelled for singlet and triplet states. Hereby, a clear picture of the detailed reaction mechanism, which directly correlates with the observed activation enthalpies and reaction orders, was gained. The superoxido formation is rate‐determining as pseudo‐first order in copper(I) although the bis‐µ‐oxido formation is observed. The results illustrate the strength of density functional theory for the prediction of the reactivity of real‐life systems.
[SiSxHy]n – Perhydridopolysilathianes: Cross‐Linked Thio Analogues of Polysiloxanes
Authors: Gerwig Maik , Schwarz Marcus , Brendler Erica , Kroke Edwin
Published: August 2016

Polysiloxane‐analogous Si–S compounds have so far not been reported. Transsilylation reactions of the solid pyridine adduct of HSiCl3 with gaseous Me3Si–S–SiMe3 yielded perhydridopolysilathianes. 29Si NMR, FTIR, and Raman spectroscopy; elemental and thermal analysis; XRD; SEM; and gas‐adsorption measurements indicated that the product consists of D‐, T‐, and Q‐units with a composition of ([H2SiS]1.2[HSiS1.5]2.6[SiS2]1.0)n. Formation of the latter is caused by pyridine‐catalyzed dismutation reactions. The polymer is mesoporous with a surface area of 187 m2 g–1; furthermore, it is amorphous and insoluble in organic solvents.
Propargyl Hydrazides as Useful Intermediates Leading to Pyrazoles via Reaction with Certain Electrophiles
Authors: Kiyokawa Kosuke , Ito Yukiteru , Kakehi Ryoma , Ogawa Takahiro , Goto Yusuke , Yoshimatsu Mitsuhiro
Published: August 2016

The reactions of propargyl hydrazides with certain electrophiles successfully led to the regioselective formation of various alkylated hydrazides. Reactions with electrophiles directly afforded the alkylated, chlorinated, brominated, and iodinated pyrazoles.
The π Complex of the Hydronium Ion Frozen on the Pathway of Electrophilic Aromatic Substitution
Authors: Růžičková Zdeňka , Holub Josef , Melichar Petr , Moncol Jan , Wann Derek A. , Fanfrlík Jindřich , Růžička Aleš , Hnyk Drahomír
Published: August 2016

A very rare crystal was prepared consisting of a 2D aromatic (toluene) together with a weakly coordinating 3D aromatic (closo‐1‐CB11H12–) and a hydronium ion, and this crystal was analyzed by using X‐ray diffraction and high‐level quantum‐mechanical calculations. The nature of the crystal arrangement made it possible to detect the frozen π complex that would originate during protonation of toluene by the acidic hydronium ion.
A Non‐enzymatic Hydrogen Peroxide Photoelectrochemical Sensor Based on a BiVO4 Electrode
Authors: Liu Min , Yu Yu‐Xiang , Zhang Wei‐De
Published: August 2016

In this study, a non‐enzymatic hydrogen peroxide photoelectrochemical (PEC) sensor based on nanoporous BiVO4 film electrode is fabricated by electrodeposit of nanoporous BiOI film on fluorine‐doped tin oxide glass (FTO) and subsequent conversion to BiVO4 by annealing at elevated temperature. The electrode exhibits excellent visible light photoelectrochemical activity, and H2O2 works as a hole scavenger to react with light‐induced electron holes on the valence band of BiVO4. Upon illumination and at applied bias potential of +0.2 V, the photocurrent density is linearly correlated to the concentration of H2O2. The linear determination range of H2O2 is 9.54–764.76 μM with a corresponding correlation coefficient of 0.9997, a detection limit of 1.59 μM (S/N=3), and sensitivity of 182.6 μA mM−1 cm−2. The optimum bias potential, most suitable film thickness, anti‐interference performance, and impedance are also explored. The sensor shows good response towards H2O2 and displays a promising prospect for non‐enzyme PEC H2O2 sensor.