bluuebunny/crossref_metadata_2025_split huggingface dataset:
Phenothiazinyl Boranes: A New Class of AIE Luminogens with Mega Stokes Shift, Mechanochromism, and Mechanoluminescence
Authors: Arivazhagan C. , Maity Arunava , Bakthavachalam K. , Jana Arijit , Panigrahi Suraj Kumar , Suresh Eringathodi , Das Amitava , Ghosh Sundargopal 
Published: April 2017

AbstractPhenothiazines with a dimesityl boron moiety, a new class of aminoboranes with B−N linkage, were synthesized. These aminoboranes exhibited interesting photophysical behavior including aggregation‐induced emission (AIE), mechanochromism (MC), mechanoluminescence (ML), and a mega Stokes shift (up to 312 nm in hexane). The solid‐state emission of the aminoboranes could be switched reversibly by grinding–fuming processes. Furthermore, the phenothiazine derivative with a bromo and an arylborane group at 3‐ and 7‐positions exhibited bright mechanoluminescence.
Probing Phosphorus Nitride (P≡N) and Other Elusive Species Formed upon Pyrolysis of Dimethyl Phosphoramidate
Authors: Liang Shuyu , Hemberger Patrick , Levalois‐Grützmacher Joëlle , Grützmacher Hansjörg , Gaan Sabyasachi 
Published: April 2017

AbstractThe thermal behavior of organophosphorus compounds is intricate and poorly understood but crucial for understanding gas‐phase flame inhibition, syntheses of thermally active phosphorus‐based reactive precursors, catalytic combustion, incineration of toxic nerve gases, and astrochemistry. In this work, the pyrolysis of dimethyl phosphoramidate was investigated using photoion photoelectron coincidence spectroscopy in combination with vacuum ultraviolet synchrotron radiation. This technique enables isomer‐selective detection of reactive intermediates, which are crucial in the understanding of the decomposition process. Combined with quantum chemical calculations, the experimental results permit the formulation of a comprehensive pyrolysis reaction pathway for dimethyl phosphoramidate, consisting of several reactive phosphorus species on four possible decomposition pathways. Compared to the decomposition of dimethyl methyl phosphonate, which leads exclusively to the formation of PO radicals, substitution of the methyl with an amino group most notably yields phosphorus nitride (P≡N). This mostly favored reaction pathway involves the subsequent loss of methanol and formaldehyde to yield three PONH2 tautomers, which eliminate water to generate P≡N. The thermally induced production of PN species and its possible role in flame inhibition has not previously been reported. In addition, the adiabatic ionization energy of O=P(OCH3)2NH2 was determined to be 9.79±0.02 eV.
Preparation and Characterization of Group 13 Cyanides
Authors: Haiges Ralf , Deokar Piyush , Vasiliu Monica , Stein Trent H. , Dixon David A. , Christe Karl O. 
Published: April 2017

AbstractBinary Group 13 cyanides [PPh4][Ga(CN)4], [PPh4]2[In(CN)5], and [PPh4]2[Tl(CN)5] were obtained in quantitative yields from the corresponding metal trifluorides MF3 (M=Ga, In, Tl) by fluoride–cyanide exchange reactions with Me3SiCN in the presence of stoichiometric amounts of [PPh4]CN in acetonitrile solution. The 2,2′‐bipyridine (bipy) adducts [(bipy)2Ga(CN)2][Ga(CN)4], [(bipy)In(CN)3], and [(bipy)Tl(CN)3] were obtained from the reaction of MF3 with Me3SiCN and bipy in acetonitrile. While the reaction of the metal trifluorides with Me3SiCN in acetonitrile resulted in recovery of the starting materials, the reaction of MF3 with Me3SiCN in pyridine (py) solution resulted in the formation of the pyridine adducts [(py)2Ga(CN)3], [(py)3In(CN)3], and [(py)2Tl(CN)3]. The cyano compounds were characterized by their vibrational spectra and, in most cases, by their X‐ray crystal structures.
The Prebiotic C‐Terminal Elongation of Peptides Can Be Initiated by N‐Carbamoyl Amino Acids
Authors: Abou Mrad Ninette , Ajram Ghinwa , Rossi Jean‐Christophe , Boiteau Laurent , Duvernay Fabrice , Pascal Robert , Danger Grégoire 
Published: April 2017

AbstractThe formation of peptides upon 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide (EDC)‐promoted activation of N‐carbamoylamino acids (CAA), was considered in the scope of our recent works on carbodiimide promoted C‐terminus elongation of peptides in a prebiotic context. Thus EDC promoted activation of CAA derivatives of Tyr(Me) or Ala in dilute aqueous medium pH 5.5–6.5 in the presence of excess of AA, resulted in peptide formation by C‐terminus activation/elongation. Kinetic results similar to those of EDC‐mediated activation of N‐acyl‐AA lead us to postulate the formation of a 2‐amino‐5(4H)‐oxazolone intermediate by cyclization of the activated CAA, in spite of the absence of epimerization occurred at CAA residues. Thus, in a prebiotic context, CAA may have played a similar role as N‐acyl‐AA in the initiation of C‐terminus peptide elongation.
High‐Throughput Optical Imaging and Spectroscopy of One‐Dimensional Materials
Authors: Yao Fengrui , Chen Cheng , Liu Can , Zhang Jin , Wang Feng , Liu Kaihui 
Published: April 2017

AbstractDirect visualization of one‐dimensional (1D) materials under an optical microscope in ambient conditions is of great significance for their characterizations and applications. However, it is full of challenges to achieve such goal due to their relative small size (ca. 1 nm in diameter) in the optical‐diffraction‐limited laser spot (ca. 1 μm in diameter). In this Concept article, we introduce a polarization‐based optical homodyne detection method that can be used as a general strategy to obtain high‐throughput, real‐time, optical imaging and in situ spectroscopy of polarization‐inhomogeneous 1D materials. We will use carbon nanotubes (CNTs) as an example to demonstrate the applications of such characterization with respect to the absorption signal of individual nanotubes, real‐time imaging of individual nanotubes in devices, and statistical structure information of nanotube arrays.
Synthesis, Structure, and Properties of Clathrate Si30.3(8)P15.7(8)Se7.930(3)
Authors: Zhang Hui , Peng Wei , Mu Gang , Hu Tao , Huang Fuqiang , Xie Xiaoming 
Published: April 2017

AbstractThe new clathrate single crystal Si30.3(8)P15.7(8)Se7.930(3) was synthesized through a solid‐state reaction, and it was characterized to have a unit cell parameter a=19.7614(1) Å and belong to space group Fm
. In this clathrate structure, a Se1−Si3 bond forms in place of the tetrakaidecahedron structure, and pental dodecahedral cages composed of Si and P atoms encapsulate Se2, Se3, and Se4 guest atoms. Similar structures are observed in partial Te‐ and Ge‐substituted compounds. Theoretical calculations based on an ordered formula Si32P14Se7 showed a semiconducting electronic structure with a band gap of 0.711 eV. A photoelectric response was observed in this compound at room temperature. Across the whole temperature range, this material exhibited a weak temperature‐dependent diamagnetic signal, and no phase transition or thermal anomaly was observed in heat capacity measurements.
Silyl Chalconium Ions: Synthesis, Structure and Application in Hydrodefluorination Reactions
Authors: Kordts Natalie , Künzler Sandra , Rathjen Saskia , Sieling Thorben , Großekappenberg Henning , Schmidtmann Marc , Müller Thomas 
Published: April 2017

AbstractThe synthesis of two series of silylated chalconium borates,9and10, which are based on theperi‐naphthyl andperi‐acenaphthyl framework, is reported (chalcogen (Ch): O, S, Se, Te). NMR investigations of the selenium‐ and tellurium‐containing precursor silanes3 d–fand8 d, frevealed a significant through‐spaceJ‐coupling between the chalcogen nuclei and the Me2SiH group. Experimental and computational results typify the synthesized cations9and10as chalconium ions. The imposed ring strain weakens the Si−Ch linkage compared to acyclic chalconium ions. This attenuation of the Si−Ch bond strength is more pronounced in the acenaphthene series. Surprisingly, the Si−O bonds in oxonium ions9 aand10 aare the weakest Si−Ch linkage in both series. The synthesized silyl chalconium borates are active in hydrodefluorination reactions of alkyl fluorides with silanes. A cooperative activation of the silane by the Lewis acidic (silicon) and by the Lewis basic side (chalcogen) is suggested.
The Surprising Importance of Peptide Bond Contacts in Drug–Protein Interactions
Authors: Parrish Robert M. , Sitkoff Doree F. , Cheney Daniel L. , Sherrill C. David 
Published: April 2017

AbstractThe study of noncovalent interactions, notably including drug–protein binding, relies heavily on the language of localized functional group contacts: hydrogen bonding, π–π interactions, CH–π contacts, halogen bonding, etc. Applying the state‐of‐the‐art functional group symmetry‐adapted perturbation theory (F‐SAPT) to an important question of chloro versus methyl aryl substitution in factor Xa inhibitor drugs, we find that a localized contact model provides an incorrect picture for the origin of the enhancement of chloro‐containing ligands. Instead, the enhancement is found to originate from many intermediate‐range contacts distributed throughout the binding pocket, particularly including the peptide bonds in the protein backbone. The contributions from these contacts are primarily electrostatic in nature, but require ab initio computations involving nearly the full drug–protein pocket system to be accurately quantified.
Structural Studies of Nicotinoids: Cotinine versus Nicotine
Authors: Uriarte Iciar , Pérez Cristóbal , Caballero‐Mancebo Elena , Basterretxea Francisco J. , Lesarri Alberto , Fernández José A. , Cocinero Emilio J. 
Published: April 2017

AbstractInvited for the cover of this issue is the group of Emilio J. Cocinero at the University of the Basque Country. The image depicts a fight between two biomolecules, cotinine and nicotine. Read the full text of the article at 10.1002/chem.201700023.
Generation of β‐Halo Vinylsulfones through a Multicomponent Reaction with Insertion of Sulfur Dioxide
Authors: Xiang Yuanchao , Kuang Yunyan , Wu Jie 
Published: April 2017

AbstractA four‐component reaction of terminal alkynes, aryldiazonium tetrafluoroborates, sulfur dioxide surrogate of DABCO⋅(SO2)2, and potassium halide in the presence of copper(I) chloride (10 mol %) gives rise to β‐halo vinylsulfones with good stereoselectivity. The vicinal difunctionalization of alkynes through sulfonylation and halogenation with the insertion of sulfur dioxide works efficiently. A plausible mechanism is proposed, which includes a radical process.
A chiral, porous, organic cage‐based, enantioselective potentiometric sensor for 2‐aminobutanol
Authors: Duan Ai‐Hong , Wang Bang‐Jin , Xie Sheng‐Ming , Zhang Jun‐Hui , Yuan Li‐Ming 
Published: April 2017

AbstractA new enantioselective potentiometric sensor containing R‐type chiral porous organic cage CC9 as the chiral selector was designed for the assay of 2‐aminobutanol. Optimized membrane electrodes displayed a linear dynamic range from 10−3 ~ 10−1 mol·L−1 with a detection limit of 2.5 × 10−4 mol·L−1 and a Nernstian response of 27 ± 0.5mV·decade−1 toward S‐2‐aminobutanol within the pH range 7.0–10.0. The potentiometric enantioselectivity coefficient (
) of this sensor was −1.333, indicating that the porous organic cage‐based electrode exhibited good discrimination toward S‐2‐aminobutanol over R‐2‐aminobutanol.
Anaerobic Digestion Model (AM2) for the Description of Biogas Processes at Dynamic Feedstock Loading Rates
Authors: Arzate Juan A. , Kirstein Max , Ertem Funda C. , Kielhorn Erich , Ramirez Malule Howard , Neubauer Peter , Cruz‐Bournazou M. Nicolas , Junne Stefan 
Published: April 2017

AbstractThe anaerobic digestion of biomass is a complex, dynamic, and highly nonlinear process. Hence, a mathematical model that is capable of describing the complete operability region with sufficient accuracy cannot be identifiable even with the most advanced process monitoring technology. The complexity of the anaerobic digestion model no. 1 (ADM1) leads to the application of either parameter‐reduced versions of the ADM1 or simpler models as, e.g., the anaerobic digestion model AM2. A comparative study for the simulation of biogas formation at dynamic feedstock loading using maize silage was performed with both models.
New Fluorescent Conjugates Displaying Solvatochromic Properties
Authors: Liu Huijing , Huang Rongrong , Fang Yu 
Published: April 2017

AbstractFour new fluorescent dyes based on bis(phenyl‐ethynyl‐)‐2‐naphthyl (BPEN) were designed and synthesized. To improve the solvatochromic property and enhance the brightness of the fluorescent BPEN, an electron‐donating unit of azetidine and/or an electron deficient group of ‐NO2 was introduced. The corresponding fluorophores are denoted as T1, T2, T3 and T4, respectively. Moreover, to facilitate derivatization of the probes, two ethoxy carbonyl residues were grafted onto the side positions of BPEN. Spectroscopic studies demonstrated that introduction of azetidine leads to superior solvatochromic properties and largely enhanced fluorescence quantum yields as evidenced by the fact that T3 shows more than 150 nm shift in its maximum emission when dissolved in solvents of very different polarities and displays high fluorescence quantum yields in the solvents studied. However, T2, which is the one bearing a ‐NO2 group, is non‐fluorescent. Theoretical analysis and Lippert‐Mataga modeling revealed the intra‐molecular charge transfer (ICT) nature of the solvatochromic behavior of the compounds. Further test reveals that the fluorophores, in particular T3, are sensitive to the presence of trace water in less polar solvents, such as THF and 1,4‐dioxane. Moreover, it is believed that the new fluorophores may serve as building blocks for creating environment‐sensitive fluorescent sensors.
High‐dose chemotherapy with thiotepa, busulfan, and cyclophosphamide and autologous stem cell transplantation for patients with primary central nervous system lymphoma in first complete remission
Authors: DeFilipp Zachariah , Li Shuli , El‐Jawahri Areej , Armand Philippe , Nayak Lakshmi , Wang Nancy , Batchelor Tracy T. , Chen Yi‐Bin 
Published: April 2017

BACKGROUNDHigh‐dose chemotherapy and autologous stem cell transplantation (HDC‐ASCT) is a therapeutic option for patients with primary central nervous system lymphoma (PCNSL). To the authors’ knowledge, data are limited regarding its use among patients in first complete remission (CR1) with the CNS‐directed conditioning regimen of thiotepa, busulfan, and cyclophosphamide (TBC).METHODSA retrospective analysis of patients with PCNSL in CR1 who underwent transplantation using a TBC‐based conditioning regimen at 2 academic institutions was performed.RESULTSForty‐six consecutive patients who underwent HDC‐ASCT while in CR1 were identified. The most common induction regimen was high‐dose methotrexate plus temozolomide and rituximab (59%). No patients received whole‐brain radiotherapy. A total of 40 patients (87%) received cytarabine before undergoing ASCT as either induction intensification, early consolidation therapy, or mobilization. The median time from diagnosis to transplantation was 6 months (range, 4‐15 months). The median age of the patients at the time of transplantation was 59 years (range, 27‐69 years). With a median follow‐up of 2.7 years after ASCT (range, 6 months‐7.5 years), the Kaplan‐Meier estimates of 2‐year overall survival and progression‐free survival were 95% (95% confidence interval [95% CI], 80%‐99%) and 92% (95% CI, 77%‐97%), respectively. The most common toxicities were severe mucositis (35%) and bacterial infections occurring within 100 days of transplantation (35%). The estimated 2‐year nonrecurrence mortality rate was 2.9% (95% CI, 0.2%‐13.4%).CONCLUSIONSHDC‐ASCT with a CNS‐directed conditioning regimen such as TBC should be considered for patients with PCNSL who are in CR1 because this approach is associated with encouraging disease control and survival in this select patient population. Cancer 2017;123:3073–79. © 2017 American Cancer Society.
Method for DNA Ploidy Analysis Along with Immunophenotyping for Rare Populations in a Sample using FxCycle Violet
Authors: Tembhare Prashant , Badrinath Yajamanam , Ghogale Sitaram , Subramanian Papagudi Ganesan 
Published: April 2017

AbstractThe clinical use of flow cytometric DNA ploidy assay has been extended towards stratifying the risk of diseases, such as monoclonal gammopathies or B cell acute lymphoblastic leukemia, and to detect circulating tumor cells, both of which require detection of minute cell populations. This unit describes a protocol for determining DNA ploidy in fixed samples with simultaneous surface immunophenotyping. It is an easy method for simultaneous 6‐ to 8‐color immunophenotyping and DNA content analysis using FxCycle Violet (FCV; DAPI) dye. This protocol is a one‐step modification of routine multicolor immunophenotyping that includes surface staining followed by fixation and then DNA staining with FCV. It utilizes mature lymphocytes from the sample as an internal control for determination of DNA index. It is a sensitive method that allows DNA‐ploidy determination and cell cycle analysis in a rare tumor population as low as 100 events, as well as DNA ploidy determination in various subsets of hematopoietic cells in the same sample based on their immunophenotype. © 2017 by John Wiley & Sons, Inc.
Bioequivalence Study of Warfarin in Healthy Chinese Volunteers With a Validated High‐Performance Liquid Chromatography‐Mass Spectrometry Method
Authors: Li Wenlong , Bu Fanlong , Li Rong , Wang Benjie , Shaikh Abdul Sami , Zhang Yunyun , Guo Ruichen , Zhang Rui 
Published: April 2017

AbstractThis study was designed to investigate the pharmacokinetics of an innovative film‐coated warfarin sodium tablet and to compare it with the marketed sugar‐coated warfarin sodium tablet in humans. A single‐dose, open‐label, randomized, two‐way crossover study was performed in 24 healthy Chinese male volunteers. They were administered 2.5 mg of innovative film‐coated warfarin sodium tablets or the marketed sugar‐coated warfarin sodium tablets. Blood samples were collected at different time points after dosing for investigation of the pharmacokinetics of warfarin in human plasma. A sensitive liquid chromatography mass spectrometry method was established to determine warfarin in plasma. Drug and Statistics 2.1.1 was applied to calculate the pharmacokinetics parameters. The main pharmacokinetic parameters for film‐coated and sugar‐coated warfarin were the following: t½, 103.5 ± 18.8 and 105.8 ± 21.3 hours; Tmax, 0.7 ± 0.5 and 1.3 ± 0.8 hours; Cmax, 347.8 ± 74.8 and 322.9 ± 75.7 ng/mL; AUC0∼360, 16,024.2 ± 3713.9 and 15,586.6 ± 3477.0 ng·mL−1·h; AUC0∼∞, 17,335.7 ± 4089.1 and 16,912.0 ± 3911.2 ng·mL−1·h, respectively. The human pharmacokinetics of film‐coated and sugar‐coated warfarin were slightly different. The oral absorption and bioavailability of innovative film‐coated warfarin were slightly higher than those of the sugar‐coated warfarin. This study is vital to clinical usage of warfarin not only because of the pharmacokinetic parameters of the 2 pharmaceutical dosage forms of warfarin but also to obtain data on the prevalence of CYP2C9 and VKORC1 genes and their influence on the concentration of warfarin.
Effect of Solvent Choice on the Self‐Assembly Properties of a Diphenylalanine Amphiphile Stabilized by an Ion Pair
Authors: Mayans Enric , Ballano Gema , Sendros Javier , Font‐Bardia Merçè , Campos J. Lourdes , Puiggalí Jordi , Cativiela Carlos , Alemán Carlos 
Published: April 2017

AbstractA diphenylalanine (FF) amphiphile blocked at the C terminus with a benzyl ester (OBzl) and stabilized at the N terminus with a trifluoroacetate (TFA) anion was synthetized and characterized. Aggregation of peptide molecules was studied by considering a peptide solution in an organic solvent and adding pure water, a KCl solution, or another organic solvent as co‐solvent. The choice of the organic solvent and co‐solvent and the solvent/co‐solvent ratio allowed the mixture to be tuned by modulating the polarity, the ionic strength, and the peptide concentration. Differences in the properties of the media used to dissolve the peptides resulted in the formation of different self‐assembled microstructures (e.g. fibers, branched‐like structures, plates, and spherulites). Furthermore, crystals of TFA⋅FF‐OBzl were obtained from the aqueous peptide solutions for X‐ray diffraction analysis. The results revealed a hydrophilic core constituted by carboxylate (from TFA), ester, and amide groups, and the core was found to be surrounded by a hydrophobic crown with ten aromatic rings. This segregated organization explains the assemblies observed in the different solvent mixtures as a function of the environmental polarity, ionic strength, and peptide concentration.
Transfection by Electroporation
Authors: Potter Huntington , Heller Richard 
Published: April 2017

AbstractElectroporation—the use of high‐voltage electric shocks to introduce DNA into cells—can be used with most cell types, yields a high frequency of both stable transformation and transient gene expression, and, because it requires fewer steps, can be easier than alternative techniques. This unit describes electroporation of mammalian cells, including ES cells, for the preparation of knock‐out, knock‐in, and transgenic mice. Protocols are described for the use of electroporation in vivo to perform gene therapy for cancer, as well as for DNA vaccination. © 2017 by John Wiley & Sons, Inc.
Gut Microbiome Standardization in Control and Experimental Mice
Authors: McCoy Kathy D. , Geuking Markus B. , Ronchi Francesca 
Published: April 2017

AbstractMouse models are used extensively to study human health and to investigate the mechanisms underlying human disease. In the past, most animal studies were performed without taking into consideration the impact of the microbiota. However, the microbiota that colonizes all body surfaces, including the gastrointestinal tract, respiratory tract, genitourinary tract, and skin, heavily impacts nearly every aspect of host physiology. When performing studies utilizing mouse models it is critical to understand that the microbiome is heavily impacted by environmental factors, including (but not limited to) food, bedding, caging, and temperature. In addition, stochastic changes in the microbiota can occur over time that also play a role in shaping microbial composition. These factors lead to massive variability in the composition of the microbiota between animal facilities and research institutions, and even within a single facility. Lack of experimental reproducibility between research groups has highlighted the necessity for rigorously controlled experimental designs in order to standardize the microbiota between control and experimental animals. Well controlled experiments are mandatory in order to reduce variability and allow correct interpretation of experimental results, not just of host‐microbiome studies but of all mouse models of human disease. The protocols presented are aimed to design experiments that control the microbiota composition between different genetic strains of experimental mice within an animal unit. © 2017 by John Wiley & Sons, Inc.
Elucidation of Intramolecular Through‐Space Electronic Communication in a Propeller‐Shaped Molecule
Authors: Kodama Takuya , Hirao Yasukazu , Nishiuchi Tomohiko , Kubo Takashi 
Published: April 2017

AbstractA novel π‐extended trinaphtho[3.3.3]propellane (TNP) derivative was prepared and through‐space electronic communication in its radical cation species was characterized by electrochemical and spectroscopic methods. Cyclic voltammetry and UV/Vis‐NIR titrations suggested weak electronic communication among the three aromatic rings. Variable‐temperature ESR measurements of the radical cation showed a drastic change in the spectra in the range of 230–180 K, indicating hopping‐type spin delocalization that would originate from migration of a counter anion.