bluuebunny/crossref_metadata_2025 huggingface dataset:
Adaptive working memory training improved brain function in human immunodeficiency virus–seropositive patients
Authors: Chang Linda , Løhaugen Gro C. , Andres Tamara , Jiang Caroline S. , Douet Vanessa , Tanizaki Naomi , Walker Christina , Castillo Deborrah , Lim Ahnate , Skranes Jon , Otoshi Chad , Miller Eric N. , Ernst Thomas M.
Published: October 2016

Objective

We aimed to evaluate the effectiveness of an adaptive working memory (WM) training (WMT) program, the corresponding neural correlates, and LMX1A‐rs4657412 polymorphism on the adaptive WMT, in human immunodeficiency virus (HIV) participants compared to seronegative (SN) controls.

Methods

A total of 201 of 206 qualified participants completed baseline assessments before randomization to 25 sessions of adaptive WMT or nonadaptive WMT. A total of 74 of 76 (34 HIV, 42 SN) completed adaptive WMT and all 40 completed nonadaptive WMT (20 HIV, 20 SN) and were assessed after 1 month, and 55 adaptive WMT participants were also assessed after 6 months. Nontrained near‐transfer WM tests (Digit‐Span, Spatial‐Span), self‐reported executive functioning, and functional magnetic resonance images during 1‐back and 2‐back tasks were performed at baseline and each follow‐up visit, and LMX1A‐rs4657412 was genotyped in all participants.

Results

Although HIV participants had slightly lower cognitive performance and start index than SN at baseline, both groups improved on improvement index (>30%; false discovery rate [FDR] corrected p < 0.0008) and nontrained WM tests after adaptive WMT (FDR corrected, p ≤ 0.001), but not after nonadaptive WMT (training by training type corrected, p = 0.01 to p = 0.05) 1 month later. HIV participants (especially LMX1A‐G carriers) also had poorer self‐reported executive functioning than SN, but both groups reported improvements after adaptive WMT (Global: training FDR corrected, p = 0.004), and only HIV participants improved after nonadaptive WMT. HIV participants also had greater frontal activation than SN at baseline, but brain activation decreased in both groups at 1 and 6 months after adaptive WMT (FDR corrected, p < 0.0001), with normalization of brain activation in HIV participants, especially the LMX1A‐AA carriers (LMX1A genotype by HIV status, cluster‐corrected‐p < 0.0001).

Interpretation

Adaptive WMT, but not nonadaptive WMT, improved WM performance in both SN and HIV participants, and the accompanied decreased or normalized brain activation suggest improved neural efficiency, especially in HIV‐LMX1A‐AA carriers who might have greater dopaminergic reserve. These findings suggest that adaptive WMT may be an effective adjunctive therapy for WM deficits in HIV participants. ANN NEUROL 2017;81:17–34
Noncovalent Functionalization of Black Phosphorus
Authors: Abellán Gonzalo , Lloret Vicent , Mundloch Udo , Marcia Mario , Neiss Christian , Görling Andreas , Varela Maria , Hauke Frank , Hirsch Andreas
Published: October 2016

Black phosphorus (BP) was functionalized with organic moieties on the basis of liquid exfoliation. The treatment of BP with electron‐withdrawing 7,7,8,8‐tetracyano‐p‐quinodimethane (TCNQ) led to electron transfer from BP to the organic dopant. On the other hand, the noncovalent interaction of BP with a perylene diimide was mainly due to van der Waals interactions but also led to considerable stabilization of the BP flakes against oxygen degradation.
Kooperative Katalyse mit N‐heterocyclischen Carbenen
Authors: Wang Michael H. , Scheidt Karl A.
Published: October 2016

Die Katalyse mit N‐heterocyclischen Carbenen (NHC) hat sich in der organischen Synthese zu einer leistungsfähigen Strategie entwickelt, um komplexe Moleküle hauptsächlich durch Umpolungsverfahren aufzubauen. Diese einzigartigen Lewis‐Basen wurden verwendet, um Acylanionen, Enolate und Homoenolate katalytisch zu generieren. Kürzlich wurde eine neue Strategie entwickelt, mit der die Anwendbarkeit der Carbenkatalyse bei Synthesen durch den wirksamen Einsatz zusätzlicher Aktivierungsarten erheblich erweitert werden konnte: die kooperative Katalyse. Durch die sorgfältige Auswahl von Cokatalysatoren können Reaktivitäten, Ausbeuten und Stereoselektivitäten verbessert werden. In einigen Fällen haben diese katalytischen Additive die Regioselektivität oder Diastereoselektivität verändert. In diesem Kurzaufsatz werden die neuesten Fortschritte bei der kooperativen Katalyse mit NHCs herausgestellt und die Gesamtentwicklung des Gebiets betrachtet.
A Thermally Populated, Perpendicularly Twisted Alkene Triplet Diradical
Authors: Wentrup Curt , Regimbald‐Krnel Michèle J. , Müller Dennis , Comba Peter
Published: October 2016

Variable‐temperature NMR and ESR spectroscopic studies reveal that bis(dibenzo[a,i]fluorenylidene) 1 possesses a singlet ground state, 1(S0), while the 90° twisted triplet 1(T1) is populated to a small extent already at room temperature. Analysis of the increasing amount of paramagnetic 1(T1) at temperatures between 300 and 500 K yields the exchange interaction Jex/h c=3351 cm−1 and a singlet–triplet energy splitting of 9.6 kcal mol−1, which is in excellent agreement with calculations (9.3 kcal mol−1 at the UKS BP86/B3LYP/revPBE level of theory). In contrast, the zero‐field splitting parameter D is very small (calculated value −0.018 cm−1) and unmeasurable.
Exploiting the Imidazolium Effect in Base‐free Ammonium Enolate Generation: Synthetic and Mechanistic Studies
Authors: Young Claire M. , Stark Daniel G. , West Thomas H. , Taylor James E. , Smith Andrew D.
Published: October 2016

N‐Acyl imidazoles and catalytic isothiourea hydrochloride salts function as ammonium enolate precursors in the absence of base. Enantioselective Michael addition–cyclization reactions using different α,β‐unsaturated Michael acceptors have been performed to form dihydropyranones and dihydropyridinones with high stereoselectivity. Detailed mechanistic studies using RPKA have revealed the importance of the “imidazolium” effect in ammonium enolate formation and have highlighted key differences with traditional base‐mediated processes.
Energetic N‐Nitramino/N‐Oxyl‐Functionalized Pyrazoles with Versatile π–π Stacking: Structure–Property Relationships of High‐Performance Energetic Materials
Authors: Yin Ping , Mitchell Lauren A. , Parrish Damon A. , Shreeve Jean'ne M.
Published: October 2016

N‐Nitramino/N‐oxyl functionalization strategies were employed to investigate structure–property relationships of energetic materials. Based on single‐crystal diffraction data, π–π stacking of pyrazole backbones can be tailored effectively by energetic functionalities, thereby resulting in diversified energetic compounds. Among them, hydroxylammonium 4‐amino‐3,5‐dinitro‐1H‐pyrazol‐1‐olate and dipotassium N,N′‐(3,5‐dinitro‐1H‐pyrazol‐1,4‐diyl)dinitramidate, with unique face‐to‐face π–π stacking, can be potentially used as a high‐performance explosive and an energetic oxidizer, respectively.
Development of a Photoactivatable Phosphine Probe for Induction of Intracellular Reductive Stress with Single‐Cell Precision
Authors: Tirla Alina , Rivera‐Fuentes Pablo
Published: October 2016

Photoactivatable phosphines that induce intracellular reductive stress are reported. The design of these probes takes advantage of the conjugate addition of trialkylphosphines to carbocyanine dyes, which can be reverted photochemically to produce the trialkylphosphine and a fluorescent reporter. The photochemical release depends on the efficiency of photoinduced electron transfer from the indolenine arm of the probe to the coumarin acceptor. These probes readily permeate the mammalian plasma membrane and can be photoactivated in live cells. Upon irradiation of the probe, the released trialkylphosphine induces intracellular reductive stress, which ultimately leads to formation of thioflavin‐positive intracellular protein aggregates. These effects could be induced in individual cells within a monolayer, with minimal disturbance of neighboring cells.
Degradation and Crystallization of Cellulose in Hydrogen Chloride Vapor for High‐Yield Isolation of Cellulose Nanocrystals
Authors: Kontturi Eero , Meriluoto Anne , Penttilä Paavo A. , Baccile Niki , Malho Jani‐Markus , Potthast Antje , Rosenau Thomas , Ruokolainen Janne , Serimaa Ritva , Laine Janne , Sixta Herbert
Published: October 2016

Despite the structural, load‐bearing role of cellulose in the plant kingdom, countless efforts have been devoted to degrading this recalcitrant polysaccharide, particularly in the context of biofuels and renewable nanomaterials. Herein, we show how the exposure of plant‐based fibers to HCl vapor results in rapid degradation with simultaneous crystallization. Because of the unchanged sample texture and the lack of mass transfer out of the substrate in the gas/solid system, the changes in the crystallinity could be reliably monitored. Furthermore, we describe the preparation of cellulose nanocrystals in high yields and with minimal water consumption. The study serves as a starting point for the solid‐state tuning of the supramolecular properties of morphologically heterogeneous biological materials.
Total Chemical Synthesis of an Intra‐A‐Chain Cystathionine Human Insulin Analogue with Enhanced Thermal Stability
Authors: Karas John A. , Patil Nitin A. , Tailhades Julien , Sani Marc‐Antoine , Scanlon Denis B. , Forbes Briony E. , Gardiner James , Separovic Frances , Wade John D. , Hossain Mohammed Akhter
Published: October 2016

Despite recent advances in the treatment of diabetes mellitus, storage of insulin formulations at 4 °C is still necessary to minimize chemical degradation. This is problematic in tropical regions where reliable refrigeration is not ubiquitous. Some degradation byproducts are caused by disulfide shuffling of cystine that leads to covalently bonded oligomers. Consequently we examined the utility of the non‐reducible cystine isostere, cystathionine, within the A‐chain. Reported herein is an efficient method for forming this mimic using simple monomeric building blocks. The intra‐A‐chain cystathionine insulin analogue was obtained in good overall yield, chemically characterized and demonstrated to possess native binding affinity for the insulin receptor isoform B. It was also shown to possess significantly enhanced thermal stability indicating potential application to next‐generation insulin analogues.
Delivering Structural Information on the Polar Face of Membrane‐Active Peptides: 19F‐NMR Labels with a Cationic Side Chain
Authors: Michurin Oleg M. , Afonin Sergii , Berditsch Marina , Daniliuc Constantin G. , Ulrich Anne S. , Komarov Igor V. , Radchenko Dmytro S.
Published: October 2016

Conformationally constrained non‐racemizing trifluoromethyl‐substituted lysine isosteres [(E)‐ and (Z)‐TCBLys] with charged side chains are presented as a new type of 19F‐NMR labels for peptide studies. Design of the labels, their synthesis, incorporation into peptides and experimental demonstration of their application for solid state NMR studies of membrane‐active peptides are described. A series of fluorine‐labeled analogues of the helical amphipathic antimicrobial peptide PGLa(Nle) was obtained, in which different lysine residues in the original peptide sequence were replaced, one at a time, by either (E)‐ or (Z)‐TCBLys. Antimicrobial activities of the synthesized analogues were practically the same as those of the parent peptide. The structural and orientational parameters of the helical PGLa(Nle) peptide in model bilayers, as determined using the novel labels confirmed and refined the previously known structure. (E)‐ and (Z)‐TCBLys, as a set of cationic 19F‐NMR labels, were shown to deliver structural information about the charged face of amphipathic peptides by solid state 19F‐NMR, previously inaccessible by this method.
A Responsive Battery with Controlled Energy Release
Authors: Wang Xiaopeng , Gao Jian , Cheng Zhihua , Chen Nan , Qu Liangti
Published: October 2016

A new type of responsive battery with the fascinating feature of pressure perceptibility has been developed, which can spontaneously, timely and reliably control the power outputs (e.g., current and voltage) in response to pressure changes. The device design is based on the structure of the Zn–air battery, in which graphene‐coated sponge serves as pressure‐sensitive air cathode that endows the whole system with the capability of self‐controlled energy release. The responsive batteries exhibit superior battery performance with high open‐circuit voltage (1.3 V), and competitive areal capacity of 1.25 mAh cm−2. This work presents an important move towards next‐generation intelligent energy storage devices with energy management function.
Donor‐Stabilized 1,3‐Disila‐2,4‐diazacyclobutadiene with a Nonbonded Si⋅⋅⋅Si Distance Compressed to a Si=Si Double Bond Length
Authors: Gau David , Nougué Raphael , Saffon‐Merceron Nathalie , Baceiredo Antoine , De Cózar Abel , Cossío Fernando P. , Hashizume Daisuke , Kato Tsuyoshi
Published: October 2016

A donor‐stabilized 1,3‐disila‐2,4‐diazacyclobutadiene presents an exceptionally short nonbonded Si⋅⋅⋅Si distance (2.23 Å), which is as short as that of Si=Si bonds (2.15–2.23 Å). Theoretical investigations indicate that there is no bond between the two silicon atoms, and that the unusual geometry can be related to a significant coulomb repulsion between the two ring nitrogen atoms. This chemical pressure phenomenon could provide an alternative and superior way of squeezing out van der Waals space in highly strained structures, as compared to the classical physical methods.
Cathepsin B‐Specific Metabolic Precursor for In Vivo Tumor‐Specific Fluorescence Imaging
Authors: Shim Man Kyu , Yoon Hong Yeol , Ryu Ju Hee , Koo Heebeom , Lee Sangmin , Park Jae Hyung , Kim Jong‐Ho , Lee Seulki , Pomper Martin G. , Kwon Ick Chan , Kim Kwangmeyung
Published: October 2016

Recently, metabolic glycoengineering with bioorthogonal click reactions has focused on improving the tumor targeting efficiency of nanoparticles as delivery vehicles for anticancer drugs or imaging agents. It is the key technique for developing tumor‐specific metabolic precursors that can generate unnatural glycans on the tumor‐cell surface. A cathepsin B‐specific cleavable substrate (KGRR) conjugated with triacetylated N‐azidoacetyl‐d‐mannosamine (RR‐S‐Ac3ManNAz) was developed to enable tumor cells to generate unnatural glycans that contain azide groups. The generation of azide groups on the tumor cell surface was exogenously and specifically controlled by the amount of RR‐S‐Ac3ManNAz that was fed to target tumor cells. Moreover, unnatural glycans on the tumor cell surface were conjugated with near infrared fluorescence (NIRF) dye‐labeled molecules by a bioorthogonal click reaction in cell cultures and in tumor‐bearing mice. Therefore, our RR‐S‐Ac3ManNAz is promising for research in tumor‐specific imaging or drug delivery.
Modification of palladium–copper thin film by reduced graphene oxide or platinum as catalyst for Suzuki–Miyaura reactions
Authors: Hoseini S. Jafar , Habib Agahi Behnaz , Samadi Fard Zahra , Hashemi Fath Roghayeh , Bahrami Mehrangiz
Published: October 2016

This study describes the synthesis of PdCu, PdCu/reduced graphene oxide and PtPdCu nanoparticle thin films via a simple reduction of organometallic precursors including [PtCl2(cod)] and [PdCl2(cod)] (cod = cis,cis‐1,5‐cyclooctadiene) complexes, in the presence of [Cu(acac)2] (acac = acetylacetonate) complex at toluene–water interface. The structure and morphology of the thin films were characterized using energy‐dispersive analysis of X‐rays, X‐ray diffraction and transmission electron microscopy techniques. Our studies show that all of these nanoparticles are suitable for the Suzuki–Miyaura coupling (SMC) reaction in water. PtPdCu and PdCu thin films showed higher catalytic activity compared to Pd thin film in the SMC reaction due to the appropriate interaction among palladium, platinum and copper metals.
Suzuki and Heck cross‐coupling reactions using ferromagnetic nanoparticle‐supported palladium complex as an efficient and recyclable heterogeneous nanocatalyst in sodium dodecylsulfate micelles
Authors: Bahrami Kiumars , Khodaei Mohammad M. , Meibodi Farhat Sadat
Published: October 2016

A novel heterogeneous Pd catalyst was synthesized by anchoring Pd(II) onto 4′‐(4‐hydroxyphenyl)‐2,2′:6′,2″‐terpyridine‐coated Fe3O4 (FMNPs@TPy‐Pd). This catalyst has been demonstrated for the first time as a recoverable and reusable heterogeneous nanocatalyst in Suzuki and Heck cross‐coupling reactions. The catalyst is very easy to handle and is environmentally safe and economical. FMNPs@TPy‐Pd was characterized using transmission and scanning electron microscopies, X‐ray diffraction, and Fourier transform infrared and energy‐dispersive X‐ray spectroscopies.
Mild and efficient Pd(PtBu3)2‐catalyzed aminocarbonylation of aryl halides to aryl amides with high selectivity
Authors: Lei Yizhu , Xiao Se , Li Guangxing , Gu Yanlong , Wu Hanfu , Shi Kaiyi
Published: October 2016

This work describes a mild and efficient approach for the synthesis of aryl amides via catalytic aminocarbonylation of aryl halides with alicyclic amines using a Pd(PtBu3)2/NH4Cl catalyst system. Under mild reaction temperature of 60°C and balloon pressure of CO, 5 mol% Pd(PtBu3)2 with a cheap NH4Cl promoter is sufficient for high yields of aryl amides. The influence of reaction parameters such as reaction temperature, ligand type and promoter on catalytic activity was investigated. This work also discusses the catalytic intermediates in detail, and provides a plausible mechanism based on an acid chloride intermediate.
Application of a novel organic nucleating agent: Cucurbit[6]uril to improve polypropylene injection foaming behavior and their physical properties
Authors: Zhou Yuhui , Gong Wei , He Li
Published: October 2016

In this study, polypropylene (PP) foams were prepared with cucurbit[6]uril (Q[6]) used as a novel nucleating agent through a microcellular injection molding foaming process. The effect of Q[6] content (0.5–2.0 wt %) on the foaming behavior, as well as thermal, rheological and mechanical characterizations of the PP/Q[6] (PQ) samples were performed. According to scanning electron microscopy (SEM) images, the microstructure of foams exhibited a smaller cell size, higher cell density, and more homogeneous distribution of cells at a higher Q[6] content. It was found that the peak temperature of crystallization, the crystallinity and the crystallization rate of PP can be obviously improved by adding a low content of Q[6] (0.25–1.0 wt %), whereas further increasing the content of Q[6] (2.0 wt %) would disfavor the effect. With increasing the Q[6] concentration, the PQ composites had higher complex viscosities at low frequencies and higher modulus than that of PP except the content of 2.0 wt %. Furthermore, the introduction of Q[6] into PP can produce a mild increase in tensile strength, flexural strength and impact strength of PQ foams. This can be due to the well dispersion of Q[6], good compatibility between PP and Q[6], as well as the improvement of the cell morphology. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44538.
Modification of the Highway Capacity Manual two‐lane highway analysis procedure for Spanish conditions
Authors: Moreno Ana T. , Llorca Carlos , Washburn Scott S. , Bessa José E. , Hale David K. , Garcia Alfredo
Published: October 2016

The US Highway Capacity Manual (HCM) methodology is used in Spain to evaluate traffic operation and quality of service. The effect of passing manoeuvre on two‐lane highway operational performance is considered through adjustment factors to average travel speeds and percent time spent following. The procedure is largely based on simulations in TWOPAS and passing behaviours observed during US calibrations in the 1970s. It is not clear whether US driving behaviour and vehicles' performance are comparable with Spanish conditions. The objective of this research is to adapt the HCM 2010 methodology to Spanish driver behaviour, for base conditions (i.e. no passing restrictions). To do so, TWOPAS was calibrated and validated based on current Spanish passing field data. The calibration used a genetic algorithm. The case study included an ideal two‐lane highway with varying directional traffic flow rate, directional split and percentage of trucks. The updated methodology for base conditions is simpler than the current HCM 2010 and does not rely on interpolation from tables. Copyright © 2016 John Wiley & Sons, Ltd.
Estimating link travel time functions for heterogeneous traffic flows on freeways
Authors: Lu Zhaoyang , Meng Qiang , Gomes Gabriel
Published: October 2016

Oversized vehicles, such as trucks, significantly contribute to traffic delays on freeways. Heterogeneous traffic populations, that is, those consisting of multiple vehicles types, can exhibit more complicated travel behaviors in the operating speed and performance, depending on the traffic volume as well as the proportions of vehicle types. In order to estimate the component travel time functions for heterogeneous traffic flows on a freeway, this study develops a microscopic traffic‐simulation based four‐step method. A piecewise continuous function is proposed for each vehicle type and its parameters are estimated using the traffic data generated by a microscopic traffic simulation model. The illustrated experiments based on VISSIM model indicate that (i) in addition to traffic volume, traffic composition has significant influence on the travel time of vehicles and (ii) the respective estimations for travel time of heterogeneous flows could greatly improve their estimation accuracy. Copyright © 2016 John Wiley & Sons, Ltd.
Methods for suspension culture, protoplast extraction, and transformation of high‐biomass yielding perennial grass Arundo donax
Authors: Pigna Gaia , Dhillon Taniya , Dlugosz Elizabeth M. , Yuan Joshua S. , Gorman Connor , Morandini Piero , Lenaghan Scott C. , Stewart C. Neal
Published: October 2016

Arundo donax L. is a promising biofuel feedstock in the Mediterranean region. Despite considerable interest in its genetic improvement, Arundo tissue culture and transformation remains arduous. The authors developed methodologies for cell‐ and tissue culture and genetic engineering in Arundo. A media screen was conducted, and a suspension culture was established using callus induced from stem axillary bud explants. DBAP medium, containing 9 µM 2,4‐D and 4.4 µM BAP, was found to be the most effective medium among those tested for inducing cell suspension cultures, which resulted in a five‐fold increase in tissue mass over 14 days. In contrast, CIM medium containing 13 µM 2,4‐D, resulted in just a 1.4‐fold increase in mass over the same period. Optimized suspension cultures were superior to previously‐described solidified medium‐based callus culture methods for tissue mass increase. Suspension cultures proved to be very effective for subsequent protoplast isolation. Protoplast electroporation resulted in a 3.3 ± 1.5% transformation efficiency. A dual fluorescent reporter gene vector enabled the direct comparison of the CAMV 35S promoter with the switchgrass ubi2 promoter in single cells of Arundo. The switchgrass ubi2 promoter resulted in noticeably higher reporter gene expression compared with that conferred by the 35S promoter in Arundo.
Randomized open-label phase II study comparing oxycodone–naloxone with oxycodone in early return of gastrointestinal function after laparoscopic colorectal surgery
Authors: Creamer F , Balfour A , Nimmo S , Foo I , Norrie J D , Williams L J , Fearon K C , Paterson H M
Published: October 2016

Background

Combined oral modified-release oxycodone–naloxone may reduce opioid-induced postoperative gut dysfunction. This study examined the feasibility of a randomized trial of oxycodone–naloxone within the context of enhanced recovery for laparoscopic colorectal resection.

Methods

In a single-centre open-label phase II feasibility study, patients received analgesia based on either oxycodone–naloxone or oxycodone. Primary endpoints were recruitment, retention and protocol compliance. Secondary endpoints included a composite endpoint of gut function (tolerance of solid food, low nausea/vomiting score, passage of flatus or faeces).

Results

Eighty-two patients were screened and 62 randomized (76 per cent); the attrition rate was 19 per cent (12 of 62), leaving 50 patients who received the allocated intervention with 100 per cent follow-up and retention (modified intention-to-treat cohort). Protocol compliance was more than 90 per cent. Return of gut function by day 3 was similar in the two groups: 13 (48 per cent) of 27 in the oxycodone–naloxone group and 15 (65 per cent) of 23 in the control group (95 per cent c.i. for difference −10·0 to 40·7 per cent; P = 0·264). However, patients in the oxycodone–naloxone group had a shorter time to first bowel movement (mean(s.d.) 87(38) h versus 111(37) h in the control group; 95 per cent c.i. for difference 2·3 to 45·4 h, P = 0·031) and reduced total (oral plus parenteral) opioid consumption (mean(s.d.) 78(36) versus 94(56) mg respectively; 95 per cent c.i. for difference −10·2 to 42·8 mg, P = 0·222).

Conclusion

High participation, retention and protocol compliance confirmed feasibility. Potential benefits of oxycodone–naloxone in reducing time to bowel movement and total opioid consumption could be tested in a randomized trial. Registration number: NCT02109640 (https://www.clinicaltrials.gov/).
Efficient and selective Palladium‐catalyzed Telomerization of 1,3‐Butadiene with Carbon Dioxide
Authors: Sharif Muhammad , Jackstell Ralf , Dastgir Sarim , Al‐Shihi Badria , Beller Matthias
Published: October 2016

A more efficient telomerization of 1,3‐butadiene with carbon dioxide leading to the valuable δ‐lactone 1 (3‐ethylidene‐6‐vinyltetrahydro‐2H‐pyran‐2‐one) is reported. The key to success is the use of a palladium/TOMPP‐catalyst system (TOMPP=tris‐(o‐methoxyphenyl)‐phosphine), which provided under optimal conditions significantly increased yields of the desired product and improved catalyst turnover numbers (TON=1500).
Experimental Characterization of a Flow‐through Pulsation Damper Regarding Pressure Pulsations and Vibrations
Authors: Koegler Andreas F. , Haselmann Daniel , Alt Nicolas S. A. , Schluecker Eberhard
Published: October 2016

Pressure attenuators, especially side branch bladder‐type accumulators, for suppression of pressure pulsations in industrial fluid applications are not suitable for higher‐pressure pulsation frequencies, e.g., with centrifugal pumps. Accumulators of the flow‐through‐type promise a faster response time and thus a wider application range. The damping performance of a flow‐through pressure accumulator with respect to fluid pressure pulsations and the resulting structure‐borne noise was investigated. The influence of varying pulsation frequencies, damper precharge pressure, and damping effect throughout the piping system was evaluated. Experiments were performed in an industrial‐scale closed‐loop test facility, with both pressure pulsations and piping vibrations in the focus. The damper, characterized by means of high‐speed video analysis, proved to be capable of damping effectively the pressure pulsations and piping vibrations induced by a centrifugal pump.
Demonstration of Controllable Electricity Production via Biogas Plants
Authors: Häring Georg , Sonnleitner Matthias , Bär Katharina , Brown Neil , Zörner Wilfried
Published: October 2016

With the expansion of renewable, but fluctuating power generation from wind and solar energy, the demand placed on the security and reliability of supply is increasing. To ensure grid stability in the future, controllable power production via biogas plants has great technical and economic potential. In order to demonstrate the operation of controllable electricity production, an existing industrial‐scale biogas plant was modified to produce electricity in accordance to the demands of the electricity market. In the course of scientific monitoring, extensive instrumentation was installed at the demonstration plant, which allows detailed evaluation of the operation of the limited gas storage volume and the behavior of the combined heat and power units (CHPs) during flexible operation.
Design Parameters for Performing Circulating Turbulent Fluidization with a Single Feed Stage Fluidized Bed Reactor
Authors: Boonprasop Sutthichai , Chalermsinsuwan Benjapon , Piumsomboon Pornpote
Published: October 2016

A fluidization reactor was designed to study the possibility of performing circulating turbulent fluidized bed (CTFB) by using only single feed gas injection. The effect of the design parameters was studied based on the Geldart classification and Archimedes number. Two sizes of sand particles represented Geldart group B, whereas a polyvinyl chloride particle represented the Geldart group A. The effect of the operating parameters was studied by manipulating the solid recirculation rates. Interpretation of the solid fraction profile along riser height could be used to determine the bed front. The appearance of CTFB in the system was indicated by the disappearance of the bed front along the riser height. A suitable riser height was lower than the maximum solid particle bed expansion; this is a crucial design parameter to support the action of CTFB.
Cobalt‐Catalyzed Reductive Cross‐Coupling Between Styryl and Benzyl Halides
Authors: Cai Yingxiao , Benischke Andreas D. , Knochel Paul , Gosmini Corinne
Published: October 2016

A simple and efficient protocol for the direct reductive cross‐coupling between alkenyl and benzyl halides using a Co/Mn system has been developed. This reaction proceeds smoothly in the presence of [CoBr2(PPh3)2] as the catalyst, with NaI as an additive in acetonitrile with a broad scope of functionalized alkenyl and benzyl halides. Different functional groups are tolerated on both coupling partners, thus, significantly extending the general scope of transition‐metal‐catalyzed benzylation of alkenyl halides. Moderate to excellent yields were also obtained. From a mechanistic point of view, a radical chain mechanism was proposed. This reaction is stereospecific and some studies suggest the retention of the double‐bond configuration.
Near‐Ultraviolet Fluorescent “ON‐OFF‐ON” Switching Sensors Based on Nitrogen‐Enriched Dual‐Color Single‐Functional Polymer Carbon Nanosheets
Authors: Wang Zhong‐Xia , Kong Fen‐Ying , Wang Wei
Published: October 2016

Graphene quantum‐dot‐like structures of highly enriched N‐based dual‐color single‐functional polymer carbon nanosheets (GLNPCNs) with an average diameter as large as 170 nm (ca. five layers) are prepared through a facile hydrothermal method. Intermolecular C5H5N5⋅⋅⋅C5H5N5 and/or C2H5OH chemical polymerization interactions in the liquid state of the peripheral crown‐ether‐like “hole”‐decorated compound GLNPCNs lead to a fascinating 2 D supramolecular polymer architecture, which exhibits near‐ultraviolet (NUV) fluorescence, ultrahigh brightness, a narrow full‐width at half‐maximum, and excellent potential for practical applications. The unique NUV fluorescence of the GLNPCNs might be attributed to the “self‐passivated” crown‐ether‐like layer on their surface; the GLNPCNs exhibit properties independent of the excitation wavelength, which is unexpected in the NUV region. Moreover, these GLNPCNs show highly selective and sensitive detection of hazardous and toxic silver (Ag+) ions, and discriminate other metal ions or anions in the range 1.5 nm to 50 μm through a fluorescence quenching response. The high sensing selectivity toward Ag+ ions could be attributable to the restricted rigid conformation of the peripheral crown‐ether‐like “hole”, which binds exclusively to the Ag+ ion. In addition to Ag+ ion sensing, the GLNPCNs quenched by Ag+ ions exhibit high selectivity and sensitivity for cysteine (Cys) in the range 2.0 nm to 50 μm through a fluorescence recovery process, which could be attributed to the effective coordination/chelation interactions between Ag+ ions and the plentiful mercapto and amino groups of Cys. Our results suggest that the facile preparation, biocompatibility, outstanding photoluminescence, and physicochemical properties of these GLNPCNs make them potentially useful in numerous applications such as bioimaging, optical and electrochemical sensors, and energy devices.
Ferrocenyl‐Coupled N‐Heterocyclic Carbene Complexes of Gold(I): A Successful Approach to Multinuclear Anticancer Drugs
Authors: Muenzner Julienne K. , Biersack Bernhard , Albrecht Alexander , Rehm Tobias , Lacher Ulrike , Milius Wolfgang , Casini Angela , Zhang Jing‐Jing , Ott Ingo , Brabec Viktor , Stuchlikova Olga , Andronache Ion C. , Kaps Leonard , Schuppan Detlef , Schobert Rainer
Published: October 2016

Four gold(I) carbene complexes featuring 4‐ferrocenyl‐substituted imidazol‐2‐ylidene ligands were investigated for antiproliferative and antivascular properties. They were active against a panel of seven cancer cell lines, including multidrug‐resistant ones, with low micromolar or nanomolar IC50 (72 h) values, according to their lipophilicity and cellular uptake. The delocalized lipophilic cationic complexes 8 and 10 acted by increasing the reactive oxygen species in two ways: through a genuine ferrocene effect and by inhibiting the thioredoxin reductase. Both complexes gave rise to a reorganization of the F‐actin cytoskeleton in endothelial and melanoma cells, associated with a G1 phase cell cycle arrest and a retarded cell migration. They proved antiangiogenic in tube formation assays with endothelial cells and vascular‐disruptive on real blood vessels in the chorioallantoic membrane of chicken eggs. Biscarbene complex 10 was also tolerated well by mice where it led to a volume reduction of xenograft tumors by up to 80 %.
ChemInform Abstract: Structure, Ionization, and Fragmentation of Hydrogenated Aluminoboron Clusters: Al2B2H2n (n = 0—6).
Authors: Muz Iskender , Canko Osman , Atis Murat
Published: October 2016

Energetic and structural stability of Al2B2H2n (n = 0—6) clusters is investigated by DFT calculations and a stochastic search algorithm.
ChemInform Abstract: Crystal Structures of the Four New Quaternary Copper(I)—Selenides A0.5CuZrSe3 and ACuYSe3 (A: Sr, Ba).
Authors: Maier Stefan , Prakash Jai , Berthebaud David , Perez Olivier , Bobev Svilen , Gascoin Franck
Published: October 2016

Single crystals of Sr0.5CuZrSe3 (I), Ba0.5CuZrSe3 (II), SrCuYSe3 (III), and BaCuYSe3 (IV) are prepared by solid state reactions of stoichiometric amounts of Cu or Cu2Se (in case of (III)), Ba or BaSe (in case of (II)), and the remaining elements (sealed silica ampoules, 1.
ChemInform Abstract: Platelike Ag2Nb4O11 Mesocrystals: Soft Chemical Synthesis, Formation Mechanism and Enhanced Photocatalytic Performance.
Authors: Kong Xingang , Guo Zhanglin , Lu Quan , Huang Jianfeng , Cao Liyun , Yin Lixiong , Li Jiayin , Feng Qi
Published: October 2016

The title mesocrystals (polycrystals of oriented nanocrystals) are prepared via a soft chemical topotactic reaction using solvothermally prepared layered K4Nb6O17 plate like particles that are first acidified by dilute HNO3 for 24 h and then subjected to an ion exchange in 0.3 M AgNO3 (24 h) which is followed by calcination in air (600 °C, 2 h).
ChemInform Abstract: Eu2(CN2)3 and KEu[Si(CN2)4]: Missing Members of the Rare Earth Metal Carbodiimide and Tetracyanamidosilicate Series.
Authors: Dutczak Danuta , Stroebele Markus , Enseling David , Juestel Thomas , Meyer H.‐Juergen
Published: October 2016

Compounds (III) and (V) are prepared by solid state metathesis reactions and characterized by powder XRD, photoluminescence, and nonlinear optical measurements.
ChemInform Abstract: A Series of New Silver Selenites with d0‐TM Cations.
Authors: Qian Qian , Kong Fang , Mao Jiang‐Gao
Published: October 2016

Compounds (IV), (VI), and (IX) are characterized by single crystal XRD and UV/Vis/near‐IR spectroscopy.
ChemInform Abstract: Cycloaddition Chemistry of Tetrafluorothiophene S,S‐Dioxide.
Authors: Lemal David M.
Published: October 2016

Tetrafluorothiophene S,S‐dioxide is found to be an all‐round partner for versatile cycloaddition reactions.
ChemInform Abstract: An Oxidative Cyclopropanation Reaction of Primary Nitro Compounds Using Fe2O3.
Authors: Moriyama Takaaki , Ito Yuji , Koyama Yusuke , Kawamoto Takuji , Kamimura Akio
Published: October 2016

Alkenylnitro compounds (I) undergo oxidative cyclopropanation by treatment with Fe2O3 in the presence of DBU and iodine.
ChemInform Abstract: Heteroarene‐Directed Oxidative sp2 C—H Bond Allylation with Aliphatic Alkenes Catalyzed by an (Electron‐Deficient η5‐Cyclopentadienyl)rhodium(III) Complex.
Authors: Takahama Yuji , Shibata Yu , Tanaka Ken
Published: October 2016

A regioselective allylation of benzenes with aliphatic olefins is achieved using heteroarenes as directing groups under mild conditions.
ChemInform Abstract: Manganese(I)‐Catalyzed Substitutive C—H Allylation.
Authors: Liu Weiping , Richter Sven C. , Zhang Yujiao , Ackermann Lutz
Published: October 2016

The first organometallic manganese‐catalyzed substitutive C—H activation for the step‐economical allylation of arenes is achieved.
ChemInform Abstract: Nickel‐Catalyzed Alkylative Cross‐Coupling of Anisoles with Grignard Reagents via C—O Bond Activation.
Authors: Tobisu Mamoru , Takahira Tsuyoshi , Morioka Toshifumi , Chatani Naoto
Published: October 2016

Ni‐catalyzed cross‐coupling of methoxy substituted naphthalene (I) with alkyl Grignard reagents offers a convenient synthesis of 2‐alkyl naphthalenes.
ChemInform Abstract: Non‐Coordinating‐Anion‐Directed Reversal of Activation Site: Selective C—H Bond Activation of N‐Aryl Rings.
Authors: Wang Dawei , Yu Xiaoli , Xu Xiang , Ge Bingyang , Wang Xiaoli , Zhang Yaxuan
Published: October 2016

A Rh‐catalyzed selective C—H bond activation of diaryl‐substituted anilides is described.
ChemInform Abstract: Metal‐Free Amidation of Carboxylic Acids with Tertiary Amines.
Authors: Phakhodee Wong , Wangngae Sirilak , Pattarawarapan Mookda
Published: October 2016

An amidation of aliphatic, allylic, and aromatic carboxylic acids with tertiary amines to give the corresponding tertiary amides is achieved under mild conditions using Ph3P—I2 as activator.
ChemInform Abstract: Electrochemical Synthesis of α‐Enaminones from Aryl Ketones.
Authors: Li Yanan , Gao Huihui , Zhang Zhenlei , Qian Peng , Bi Meixiang , Zha Zhenggen , Wang Zhiyong
Published: October 2016

An electrochemical, oxidative three‐component coupling reaction of aromatic ketones, cyclic amines, and nitroacetate affords α‐enaminones under mild conditions in good yields.
ChemInform Abstract: Reductive Etherification of Fatty Acids or Esters with Alcohols Using Molecular Hydrogen.
Authors: Erb Benjamin , Risto Eugen , Wendling Timo , Goossen Lukas J.
Published: October 2016

The environmentally benign, robust, solvent‐free conditions render the protocol attractive for the title transformation of complex molecules.
ChemInform Abstract: Chiral Integrated Catalysts Composed of Bifunctional Thiourea and Arylboronic Acid: Asymmetric Aza‐Michael Addition of α,β‐Unsaturated Carboxylic Acids.
Authors: Hayama Noboru , Azuma Takumi , Kobayashi Yusuke , Takemoto Yoshiji
Published: October 2016

A range of enantioenriched β‐(benzyloxy)amino acid derivatives are prepared in high yields and with high enantioselectivities.
ChemInform Abstract: Palladium‐Catalyzed Directed para C—H Functionalization of Phenols.
Authors: Patra Tuhin , Bag Sukdev , Kancherla Rajesh , Mondal Anirban , Dey Aniruddha , Pimparkar Sandeep , Agasti Soumitra , Modak Atanu , Maiti Debabrata
Published: October 2016

The directing‐group‐assisted para C—H functionalization of toluene derivatives occurs under assistance of a recyclable silicon‐containing biphenyl‐based template.
ChemInform Abstract: Nucleophilic Nitration of Arynes by Sodium Nitrite and Its Multicomponent Reaction Leading to Double‐Functionalized Arenes.
Authors: Dhokale Ranjeet A. , Mhaske Santosh B.
Published: October 2016

An unusual nucleophilic nitration of arynes, generated by Kobayashi′s method, is studied.
ChemInform Abstract: Facile Synthesis of Photoactive Diaryl(hetaryl)cyclopentenes by Ionic Hydrogenation.
Authors: Lvov Andrey G. , Bulich Ekaterina Yu. , Metelitsa Anatoly V. , Shirinian Valerii Z.
Published: October 2016

Unsymmetrical photoswitchable diarylethenes containing benzene, thiophene, or azoles as aromatic moieties are prepared.
ChemInform Abstract: One‐Pot Synthesis of Tetraphene and Construction of Expanded Conjugated Aromatics.
Authors: Wang Jianbo , Yao Jinzhong , Wang Hailong , Chen Hao , Dong Jingcheng , Zhou Hongwei
Published: October 2016

The method comprises a multi‐step sequence consisting of a propargyl‐allenyl isomerization, phosphine addition, Wittig and Diels‐Alder reactions in an operationally simple one‐pot manner.
ChemInform Abstract: Tandem Olefin Metathesis/Oxidative Cyclization: Synthesis of Tetrahydrofuran Diols from Simple Olefins.
Authors: Dornan Peter K. , Lee Daniel , Grubbs Robert H.
Published: October 2016

A one‐pot tandem process consisting of an olefin metathesis step and an oxidative cyclization is developed to construct 2,5‐disubstituted tetrahydrofurans in a highly stereocontrolled manner.
ChemInform Abstract: Carbazole Annulation via Cascade Nucleophilic Addition—Cyclization Involving 2‐(Silyloxy)pentadienyl Cation.
Authors: Stepherson Jacob R. , Ayala Caitlan E. , Tugwell Thomas H. , Henry Jeffrey L. , Fronczek Frank R. , Kartika Rendy
Published: October 2016

A new strategy toward the synthesis of highly functionalized carbazoles under Broensted acid catalysis is developed.
ChemInform Abstract: Palladium‐Catalyzed Carbonylation of β‐Arylethylamide Directed by Oxalyl Amide in the Presence of Carbon Monoxide.
Authors: Zhang Li , Wang Chao , Han Jian , Huang Zhi‐Bin , Zhao Yingsheng
Published: October 2016

The scalable title reaction offers access to various 3,4‐dihydroisoquinoline derivatives in high yields.
ChemInform Abstract: Visible Light Driven Photocascade Catalysis: Ru(bpy)3(PF6)2/TBHP‐Mediated Synthesis of Fused β‐Carbolines in Batch and Flow Microreactors.
Authors: Chandrasekhar D. , Borra Satheesh , Nanubolu Jagadeesh Babu , Maurya Ram Awatar
Published: October 2016

A series of fused β‐carbolines are synthesized based on a photoredox‐catalyzed [3 + 2] cycloaddition strategy.
ChemInform Abstract: Palladium‐Catalyzed ipso‐Borylation of Aryl Sulfides with Diborons.
Authors: Bhanuchandra M. , Baralle Alexandre , Otsuka Shinya , Nogi Keisuke , Yorimitsu Hideki , Osuka Atsuhiro
Published: October 2016

Inherently reluctant C—S bonds are transferred into C—B bonds in a catalytic Miyaura‐type reaction.
ChemInform Abstract: Diverse Asymmetric Hydrofunctionalization of Aliphatic Internal Alkenes Through Catalytic Regioselective Hydroboration.
Authors: Xi Yumeng , Hartwig John F.
Published: October 2016

A highly enantio‐ and regioselective Cu‐catalyzed hydroboration of alkenes is developed.
ChemInform Abstract: Structural Analogues of Selfotel.
Authors: Dziuganowska Zofia A. , Slepokura Katarzyna , Volle Jean‐Noel , Virieux David , Pirat Jean‐Luc , Kafarski Pawel
Published: October 2016

Several analogues of the NMDA receptor antagonist selfotel are synthesized and tested for their biological activity.
ChemInform Abstract: Cynotophyllosides K—L from the Roots of Cynanchum otophyllum.
Authors: Pang Wei‐Wei , Zheng Yang , Qian Hao‐Ying , Ma Lie‐Feng , Wang Fa‐Song , Shan Wei‐Guang , Zhan Zha‐Jun
Published: October 2016

Two new steroidal glycosides, cynotophyllosides K (I) and L (II), are isolated from the roots of Cynanchum otophyllum together with three known steroids.
ChemInform Abstract: Downconversion from Ultra Violet to Near Infer Red Region in Novel Yb3+ Doped LiSrVO4 Phosphor.
Authors: Sawala N. S. , Omanwar S. K.
Published: October 2016

White polycrystalline powders of LiSr1‐xVO4:Ybx (x = 0—0.01) are prepared by co‐precipitation from stoichiometric solutions of LiNO3, Sr(NO3)2, and Yb2O3 in HNO3 to which an aqueous solution of NH4VO3 is given followed by a final heating of the dried precursor (500 and 600 °C, 1 h each).
ChemInform Abstract: Specific Features of the Structures of Monomeric Octahedral D2 Rhenium(V) Oxo Complexes with Oxygen Atoms trans to the Oxo Ligands: Complexes with Neutral Ligands OER3 (E: P, As; R3: Ph3, PhEt2) trans to O(oxo)
Authors: Sergienko V. S.
Published: October 2016

Review: 42 refs.
ChemInform Abstract: Tuning the Topology of Hybrid Inorganic—Organic Materials Based on the Study of Flexible Ligands and Negative Charge of Polyoxometalates: A Crystal Engineering Perspective
Authors: Taleghani Somayeh , Mirzaei Masoud , Eshtiagh‐Hosseini Hossein , Frontera Antonio
Published: October 2016

Review: 159 refs.
ChemInform Abstract: Cyclic Dinucleotide (c‐di‐GMP, c‐di‐AMP, and cGAMP) Signalings Have Come of Age to Be Inhibited by Small Molecules
Authors: Opoku‐Temeng Clement , Zhou Jie , Zheng Yue , Su Jianmei , Sintim Herman O.
Published: October 2016

Review: 173 refs.
ChemInform Abstract: Ring‐Closing Metathesis in Peptides
Authors: Gleeson Ellen C. , Jackson W. Roy , Robinson Andrea J.
Published: October 2016

Review: 119 refs.
ChemInform Abstract: Nucleophile Selective Cross‐coupling Reactions on Aromatic Rings: A New Tool in the Synthetic Chemist′s Tool Box
Authors: Staubitz A. , Linshoeft J. , Heinrich A. C. J.
Published: October 2016

Review: 11 refs.
ChemInform Abstract: Methods of Assembling 3‐Azabicyclo[3.1.0]hexane Skeleton
Authors: Ershov Oleg V. , Bardasov Ivan N.
Published: October 2016

Review: [8 refs.
ChemInform Abstract: Advances in the Development of Catalytic Tethering Directing Groups for C—H Functionalization Reactions
Authors: Sun Huan , Guimond Nicolas , Huang Yong
Published: October 2016

Review: [40 refs.
ChemInform Abstract: Chemical Insight into the Mechanism and Specificity of GlfT2, a Bifunctional Galactofuranosyltransferase from Mycobacteria
Authors: Poulin Myles B. , Lowary Todd L.
Published: October 2016

Review: 56 refs.
ChemInform Abstract: Porous Nanomaterials as Green Catalyst for the Conversion of Biomass to Bioenergy
Authors: Bhanja Piyali , Bhaumik Asim
Published: October 2016

Review: 141 refs.
ChemInform Abstract: Metal—Organic Frameworks as Competitive Materials for Non‐Linear Optics
Authors: Mingabudinova L. R. , Vinogradov V. V. , Milichko V. A. , Hey‐Hawkins E. , Vinogradov A. V.
Published: October 2016

Review: 124 refs.
ChemInform Abstract: Molecularly Imprinting: a Tool of Modern Chemistry for Analysis and Monitoring of Phenolic Environmental Estrogens
Authors: Xie Xiaoyu , Bu Yusi , Wang Sicen
Published: October 2016

Review: 84 refs.
Brauwissenschaft und Brauereitechnologie
Authors: Narziss Ludwig , Back Werner
Published: October 2016

Das deutsche Reinheitsgebot setzt der deutschen Brauindustrie enge Grenzen bei der Bierproduktion. Die zugelassenen Rohstoffe sind Malz, Wasser, Hopfen und Hefe. Zur Steuerung der Prozesse stehen den Brauereien daher nur Betriebsparameter wie Temperatur, Zeit, pH und Druck zur Verfügung. Durch Grundlagenforschung der Enzymreaktionen, der Abbauvorgänge und der Beeinflussungsfaktoren konnte der Brauvorgang optimiert und beschleunigt werden. Eine besondere Bedeutung kommt der Züchtung von immer höher qualifizierten Rohstoffen, aber auch der Auswahl und Beschreibung von unter‐ und obergärigen Hefestämmen zu.
Extraktive Gewinnung von Germanium aus pflanzlicher Biomasse
Authors: Schreiter Norbert , Aubel Ines , Bertau Martin
Published: October 2016

Germanium ist ein strategisches Halbmetall, dessen Versorgungssicherheit als kritisch eingestuft wird. Typischerweise wird es aus Nebenprodukten der Zinkverhüttung gewonnen. Ein gänzlich neuer Ansatz ist die Germaniumgewinnung aus Pflanzen (Phytomining). Mit der Integration der Wertmetallgewinnung in die Prozesskette der Biogasproduktion wird eine vollständige Verwertung der pflanzlichen Rohstoffe erreicht. Dies gelang durch saure Laugung der Biomasse und anschließende Extraktion auf Germanium. Die Begleitmetalle werden zu ≥ 95 % abgetrennt und das Germanium bei anschließender Destillation über GeCl4 als GeO2 hydrolysiert.