bluuebunny/crossref_metadata_2025 huggingface dataset:
Selektive Übertragung eines Stickstoffatoms im [CeON]+/CH4‐System durch hocheffizientes Intersystem Crossing
Authors: Zhou Shaodong , Sun Xiaoyan , Yue Lei , Guo Cheng , Schlangen Maria , Schwarz Helmut
Published: October 2018

Die thermischen Reaktionen von [CeON]+ mit Methan wurden mithilfe von FT‐ICR‐Massenspektrometrie und quantenchemischen Rechnungen untersucht. Als einziger Reaktionspfad wurde die Übertragung eines Stickstoffatoms vom Cluster‐Ion auf Methan beobachtet. Laut Rechnungen handelt es sich bei dem gebildeten Neutralmolekül entweder um CH2NH2 oder um CH3NH. Außer durch die relativ schwache OCe+‐N‐Bindung wird diese Reaktion auch von einem hocheffizienten Intersystem Crossing angetrieben. Mechanistische Aspekte und die damit verbundenen elektronischen Ursachen werden diskutiert, und ein detaillierter Vergleich von [CeON]+, [CeO]+, [CeN]+, [CeO2]+ und atomarem Stickstoff in deren Reaktionen mit CH4 wird geliefert.
Enantioselective Synthesis of Chiral‐at‐Sulfur 1,2‐Benzothiazines by CpxRhIII‐Catalyzed C−H Functionalization of Sulfoximines
Authors: Sun Yang , Cramer Nicolai
Published: October 2018

Sulfoximines with stereogenic sulfur atoms are attractive structural motifs in drug discovery. A direct catalytic enantioselective method for the synthesis of sulfur‐chiral 1,2‐benzothiazines from readily accessible diaryl sulfoximines is presented. Rhodium(III) complexes equipped with chiral cyclopentadienyl ligands and paired with suitable carboxylic acid additives engage in an enantiodetermining C−H activation directed by the sulfoximine group. Subsequent trapping of the rhodacycle with a broad range of diazoketones gives access to S‐chiral 1,2‐benzothiazines with synthetically highly attractive substitution patterns in good yields and enantioselectivities.
Substrate‐Induced Self‐Assembly of Cooperative Catalysts
Authors: Solís Muñana Pablo , Ragazzon Giulio , Dupont Julien , Ren Chloe Z.‐J. , Prins Leonard J. , Chen Jack L.‐Y.
Published: October 2018

Dissipative self‐assembly processes in nature rely on chemical fuels that activate proteins for assembly through the formation of a noncovalent complex. The catalytic activity of the assemblies causes fuel degradation, resulting in the formation of an assembly in a high‐energy, out‐of‐equilibrium state. Herein, we apply this concept to a synthetic system and demonstrate that a substrate can induce the formation of vesicular assemblies, which act as cooperative catalysts for cleavage of the same substrate.
Defined High Molar Mass Poly(2‐Oxazoline)s
Authors: Monnery Bryn D. , Jerca Valentin V. , Sedlacek Ondrej , Verbraeken Bart , Cavill Rachel , Hoogenboom Richard
Published: October 2018

Poly(2‐alkyl‐2‐oxazoline)s (PAOx) are regaining interest for biomedical applications. However, their full potential is hampered by the inability to synthesise uniform high‐molar mass PAOx. In this work, we proposed alternative intrinsic chain transfer mechanisms based on 2‐oxazoline and oxazolinium chain‐end tautomerisation and derived improved polymerization conditions to suppress chain transfer, allowing the synthesis of highly defined poly(2‐ethyl‐2‐oxazoline)s up to ca. 50 kDa (dispersity (Ð) <1.05) and defined polymers up to at least 300 kDa (Ð<1.2). The determination of the chain transfer constants for the polymerisations hinted towards the tautomerisation of the oxazolinium chain end as most plausible cause for chain transfer. Finally, the method was applied for the preparation of up to 60 kDa molar mass copolymers of 2‐ethyl‐2‐oxazoline and 2‐methoxycarbonylethyl‐2‐oxazoline.
Cherenkov Radiation‐Mediated In Situ Excitation of Discrete Luminescent Lanthanide Complexes
Authors: Cosby Alexia G. , Ahn Shin Hye , Boros Eszter
Published: October 2018

Lanthanide luminescence, while ideal for in vivo applications owing to sharp emission bands within the optical window, requires high‐intensity, short‐wavelength excitation of small organic “antenna” chromophores in the vicinity of the lanthanide complex to access excited f‐orbital states through intersystem crossing. Herein, we explored Cherenkov radiation of the radioisotopes 18F and 89Zr as an in situ source of antenna excitation. The effective inter‐ and intramolecular excitation of the terbium(III) complexes of a macrocylic polyaminocarboxylate ligand (hydration number (q)=0, quantum yield (φ)=47 %) as well as its analogue functionalized to append an intramolecular Cherenkov excitation source (q=0.07, φ=63 %) was achieved. Using conventional small‐animal fluorescence imaging equipment, we have determined a detection limit of 2.5 nmol of Tb(III) complex in presence of 10 μCi of 18F or 89Zr. Our system is the first demonstration of the optical imaging of discrete luminescent lanthanide complexes without external short‐wave excitation.
4‐(4‐Propylpiperazine‐1‐yl)butane‐1‐sulfonic acid‐modified silica‐coated magnetic nanoparticles: A novel and recyclable catalyst for the synthesis of 5‐arylidinebarbituric acids and pyrano[2,3‐d]pyrimidinedione derivatives in aqueous media
Authors: Pourghasemi‐Lati M. , Shirini F. , Alinia‐Asli M. , Rezvani M.A.
Published: October 2018

A mild, simple and efficient procedure for the preparation of barbituric acid and pyrano[2,3‐d]pyrimidine derivatives in aqueous media is described using 4‐(4‐propylpiperazine‐1‐yl)butane‐1‐sulfonic acid‐modified silica‐coated magnetic nanoparticles as a novel and reusable catalyst. The catalyst was easily isolated from the reaction mixture by magnetic decantation using an external magnet and reused at least eight times without significant degradation in activity.
Combined Esterification and Short‐Path Distillation for High‐Purity Pentaerythritol Ester from Palm Kernel for Biolubricants
Authors: Abd Maurad Zulina , Yeong Shoot Kian , Idris Zainab , Ishak Siti Afida
Published: October 2018

The development of specialty esters using palm‐based materials through a solventless and autocatalytic method was investigated. The C8−C10 fatty‐acid esters of pentaerythritol are the bases for high‐performance lubricants. In the present study, an easy and efficient method was developed using an esterification process coupled with short‐path distillation to produce high‐purity pentaerythritol ester (PEE) for the more complete removal of acid value (AV) in the end products. The compositions of the distilled PEE have the highest 96% w/w % tetraester at an evaporator temperature of 200–225 °C and a vacuum pressure of 0.05 mbar to retain a low AV of less than 1 mg KOH g−1 and a low hydroxyl value. The rate of heating at 30 °C h−1 was found to be crucial in obtaining high‐purity tetraester. According to Organization for Economic Cooperation and Development (OECD) 301F, PEE is readily biodegradable and 100% biodegradability can be achieved in less than 9 days. PEE produced has shown lubricant properties and can be used as a base stock for biolubricant composition.
Genetic Inactivation of ZCCHC6 Suppresses Interleukin‐6 Expression and Reduces the Severity of Experimental Osteoarthritis in Mice
Authors: Ansari Mohammad Y. , Khan Nazir M. , Ahmad Nashrah , Green Jonathan , Novak Kimberly , Haqqi Tariq M.
Published: October 2018

Objective

Cytokine expression is tightly regulated posttranscriptionally, but high levels of interleukin‐6 (IL‐6) in patients with osteoarthritis (OA) indicate that regulatory mechanisms are disrupted in this disorder. The enzyme ZCCHC6 (zinc‐finger CCHC domain–containing protein 6; TUT‐7) has been implicated in posttranscriptional regulation of inflammatory cytokine expression, but its role in OA pathogenesis is unknown. The present study was undertaken to investigate whether ZCCHC6 directs the expression of IL‐6 and influences OA pathogenesis in vivo.

Methods

Human and mouse chondrocytes were stimulated with recombinant IL‐1β. Expression of ZCCHC6 in human chondrocytes was knocked down using small interfering RNAs. IL‐6 transcript stability was determined by actinomycin D chase, and 3′‐uridylation of microRNAs was determined by deep sequencing. Zcchc6−/− mice were produced by gene targeting. OA was surgically induced in the knee joints of mice, and disease severity was scored using a semiquantitative grading system.

Results

ZCCHC6 was markedly up‐regulated in damaged cartilage from human OA patients and from wild‐type mice with surgically induced OA. Overexpression of ZCCHC6 induced the expression of IL‐6, and its knockdown reduced IL‐6 transcript stability and IL‐1β–induced IL‐6 expression in chondrocytes. Reintroduction of Zcchc6 in Zcchc6−/− mouse chondrocytes rescued the IL‐1β–induced IL‐6 expression. Knockdown of ZCCHC6 reduced the population of micro‐RNA 26b (miR‐26b) with 3′‐uridylation by 60%. Zcchc6−/− mice with surgically induced OA produced low levels of IL‐6 and exhibited reduced cartilage damage and synovitis in the joints.

Conclusion

These findings indicate that ZCCHC6 enhances IL‐6 expression in chondrocytes through transcript stabilization and by uridylating miR‐26b, which abrogates repression of IL‐6. Inhibition of IL‐6 expression and significantly reduced OA severity in Zcchc6−/− mice identify ZCCHC6 as a novel therapeutic target to inhibit disease pathogenesis.
Divergent Dynamic Kinetic Resolution of a Racemic Mixture of Four Stereoisomers via N‐Heterocyclic Carbene Organocatalysis
Authors: Vasamsetty Laxmaiah , Kong Xiangwen , Meng Miao , Yang Shuang , Xu Weici , Reddy Pogula Sreekanth , Fang Xinqiang
Published: October 2018

Racemic mixtures of four stereoisomers are easily formed via many fundamental organic transformations, but the direct utilities of these mixtures have been less studied and remain large challenges to date. In this work, we introduce a new method, i.e., divergent dynamic kinetic resolution, to achieve the separation of racemic mixtures of four stereoisomers. The hypothesis was proved by using a N‐heterocyclic carbene‐catalyzed benzoin reaction, which afforded two separable diastereomeric products bearing three consecutive stereocenters with good to excellent enantioselectivties. We believe that this resolution protocol will find applications in more transformations.
Mixed Event‐Triggered Mechanism Modeling and Controlling for Networked Control Systems with Time‐Varying Delays and Uncertainties
Authors: Liu Bin , Liu Yicai
Published: October 2018

This paper is concerned with modeling and controlling under the mixed event‐triggered mechanism (ETM) for networked control systems (NCSs) with time‐varying delays and uncertainties. Firstly, an event‐triggered threshold is set by using both state and state‐independent informations in the mixed ETM. Then the event‐triggered NCSs with network‐induced time‐varying delays which exist in both sensor‐to‐controller and controller‐to‐actuator channels are modeled as a general time‐delay system. Based on the piecewise differentiable characteristic of the time‐varying delay and by using the approach of free weighting matrix and reciprocally convex, a less conservative criterion to be globally uniformly ultimately bounded (GUUB) stability and a controller design method are derived. Furthermore, an algorithm is proposed to obtain the desired mixed ETM and state‐feedback controller which can render the network load and control performance to reach an expected level. Compared with the relative and absolute ETMs, the proposed mechanism can effectively improve the transmission efficiency during the whole working time. Finally, a numerical example is given to show the effectiveness of the proposed approach.
Understanding the Reaction Interface in Lithium‐Oxygen Batteries
Authors: Huang Jun , Peng Zhangquan
Published: October 2018

The presented review article recapitulates the current state of the art in understanding three fundamental issues relevant to the reaction interface in lithium‐oxygen batteries; i) charge transport across lithium peroxide, ii) morphological evolution and identification of reactive sites, and iii) mechanisms of the involved oxygen reactions. Except of the discharge reaction mechanism, there is still a lack of a complete mechanistic picture for these fundamental issues. However, we are standing at the brink of connecting the single dots to draw the overall image. Neglect of double layer effects and nonlinearities has led us to stray from the path towards correct understanding of the charge transport. The current status of reaction sites reminds us of the parable of the blind and the elephant. Multiple in‐situ, cross‐validated methods and multiple working hypotheses are essential for a comprehensive understanding. More efforts, especially on identifying the reaction intermediates, are required to portray a unifying mechanistic scheme for the charge reaction mechanism.
Chlorophyllin supplementation modulates hyperglycemia‐induced oxidative stress and apoptosis in liver of streptozotocin‐administered mice
Authors: Patar Abani Kumar , Sharma Anupama , Syiem Donkupar , Bhan Surya
Published: October 2018

Chlorophyllin is a water‐soluble mixture of sodium–copper salts of chlorophyll with antioxidant and antimutagen properties. In this study, an attempt has been made to evaluate the effect of chlorophyllin on hyperglycemia‐induced oxidative stress and apoptosis in liver of streptozotocin (STZ)‐administered mice. In STZ‐induced diabetes, two causative factors for pancreatic β‐cell deaths are DNA alkylation and profound reactive oxygen species (ROS) generation. In this study, chlorophyllin treatment was found to be able to modulate oxidative stress and apoptosis in liver of diabetic mice. Diabetic mice exhibited a significant reduction of ROS, malondialdehyde (MDA), and protein carbonyl levels upon treatment with the chlorophyllin. However, antioxidant enzymes, such as copper–zinc superoxide dismutase (CuZnSOD), manganese superoxide dismutase (MnSOD), and catalase (CAT) showed enhanced activity as well as expression in chlorophyllin‐administered diabetic mice. The hepatoprotective effect of chlorophyllin was confirmed from the decreased activity of aspartate aminotransferase (AST), alanine aminotransferase (ALT), and alkaline phosphatase (ALP). The histological and ultrastructural studies revealed the ability of chlorophyllin to restore morphological and cellular alterations as observed in STZ‐induced diabetic mice. The effect of chlorophyllin on apoptosis showed the downregulation of cysteine‐dependent aspartate‐specific protease (caspase) 3 and caspase 9, whereas upregulation of B‐cell lymphoma‐2 (Bcl‐2) protein, and the terminal deoxynucleotidyl transferase (TdT)‐mediated dUTP nick‐end labeling (TUNEL) assay demonstrated a few apoptotic cells. In conclusion, it can be stated that chlorophyllin treatment can exert hepatoprotective effect via modulating hyperglycemia‐induced oxidative stress and apoptosis in STZ‐administered diabetic mice. © 2018 BioFactors, 44(5):418–430, 2018
Pharmacokinetics of monoester‐diterpenoid alkaloids in myocardial infarction and normal rats after oral administration of Sini decoction by microdialysis combined with liquid chromatography–tandem mass spectrometry
Authors: Zhou Qian , Meng Ping , Wang Haibo , Dong Xin , Tan Guangguo
Published: October 2018

Monoester‐diterpenoid alkaloids are the main bioactive components of Sini decoction, which is a well‐known traditional Chinese medicine formula for the treatment of myocardial infarction (MI) and heart failure in China. In this work, an ultra‐high‐performance liquid chromatography–mass spectrometry combined with microdialysis method was successfully established and applied for investigating for the first time comparative plasma pharmacokinetics of three monoester‐diterpenoid alkaloids (benzoylmesaconitine, benzoylaconitine and benzoylhypacoitine) in normal and MI rats after oral administration of Sini decoction. The statistical results of pharmacokinetic parameters demonstrated that benzoylmesaconitine, benzoylaconitine and benzoylhypacoitine showed lower peak concentration, longer half‐life, smaller area under the concentration–time curve, slower clearance, time to peak concentration and mean residence time in MI rats than in normal rats (p < 0.05), which indicated that monoester‐diterpenoid alkaloids exhibited lower systemic exposure and slower elimination in the MI rats. The results provided the experimental basis for understanding the metabolic fate and therapeutic effects of Sini decoction.
The anatomy of urination: What every physician should know
Authors: Weledji Elroy P. , Eyongeta Divine , Ngounou Eleanor
Published: October 2018

Normal voiding needs a coordinated, sustained bladder contraction of adequate size and duration. It requires a decrease in resistance of the bladder neck and urethra and no obstruction. Voiding problems can arise from abnormal storage of urine or problems with urinary control. The aim of this article was to review the functional anatomy and physiology of urinary control and micturition and the pathophysiology of urinary control problems. The Medline (PubMed) database, Cochrane Library, and Science Citation Index were searched electronically to identify original published studies on bladder anatomy, function and urinary control. References were searched from relevant chapters in specialized texts and all were included. Voiding problems are the most common presenting urological symptoms in general medical practice. Urinary incontinence occurs when the normal process of storing and passing urine is disrupted. A history of coexisting fecal incontinence suggests a neuropathic etiology. A better understanding of the physiology of urinary control could lead to preventive measures for postoperative urinary retention and incontinence such as fluid restriction and to appropriate anesthesia/analgesia, autonomic nerve preservation, total mesorectal excision (TME) for rectal cancer, and biofeedback exercises. It could also suggest appropriate therapeutic measures for established urinary incontinence. Clin. Anat., 2018. © 2018 Wiley Periodicals, Inc.
CTHRC1 overexpression predicts poor survival and enhances epithelial‐mesenchymal transition in colorectal cancer
Authors: Ni Shujuan , Ren Fei , Xu Midie , Tan Cong , Weng Weiwei , Huang Zhaohui , Sheng Weiqi , Huang Dan
Published: October 2018

Collagen triple helix repeat containing (CTHRC1), which was identified as a cancer‐related factor, is a promigratory protein involved in multiple processes, including vascular remodeling, antifibrosis, metabolism, bone formation, and cancer. In this study, we aimed to investigate the clinical significance and possible role of CTHRC1 in the process of epithelial‐mesenchymal transition (EMT) in colorectal cancer (CRC). Here, we revealed that CTHRC1 mRNA and protein levels are both upregulated in CRC tissues compared with those of paired noncancerous tissues. Moreover, the overexpression of CTHRC1 correlated with poor prognosis in patients with CRC (especially colon cancer). Furthermore, we showed that CTHRC1 induced EMT and promoted cell motility in CRC cells. Importantly, we demonstrated that CTHRC1 promoted EMT by activating transforming growth factor‐β (TGF‐β) signaling, revealing a possible effective therapeutic treatment for patients with CRC.
The role of tissue and serum carcinoembryonic antigen in stages I to III of colorectal cancer—A retrospective cohort study
Authors: Tong Guojun , Xu Wei , Zhang Guiyang , Liu Jian , Zheng Zhaozheng , Chen Yan , Niu Pingping , Xu Xuting
Published: October 2018

Purpose

Tissue carcinoembryonic antigen (t‐CEA) and serum carcinoembryonic antigen (s‐CEA) expression profiles are the most useful tumor markers for the diagnosis and evaluation of colorectal cancer (CRC) worldwide; however, their roles in CRC progression remain controversial. This study aimed to compare the prognostic values of both s‐CEA and t‐CEA in CRC.

Methods

A total of 517 patients from January 2006 to December 2010 with stages I‐III CRC were retrospectively examined, with 5‐year postoperative follow‐up and death as end‐points. T‐CEA expression, s‐CEA expression, and clinical pathological parameters were inputted into the SPSS 21.0 software. The Kaplan‐Meier method was used to analyze the 5‐year disease‐free survival (DFS) rate of patients in different tumor node metastasis (TNM) stages based on t‐CEA and s‐CEA expression.

Results

Tumor differentiation and the number of positive lymph node harvests were significantly different among the t‐CEA groups (P < 0.001, P = 0.002); however, clinicopathological features showed no significant difference. The groups with high s‐CEA and t‐CEA expression had a significantly poorer prognosis than those with low s‐CEA (P = 0.021) and t‐CEA (P < 0.01) expression, respectively. The multivariate analysis demonstrated that t‐CEA was an independent prognostic factor in CRC (P < 0.001), but s‐CEA was not (P = 0.339). The 5‐year disease‐free survival rates among the t‐CEA groups were significantly different in stages I, II, and III of CRC (P = 0.001, P < 0.001, P < 0.001), whereas in the s‐CEA groups, this difference was observed only in stage III (P = 0.014).

Conclusion

This study shows that postoperative t‐CEA expression is an independent factor associated with poorer CRC prognosis and has a higher prognostic value than that of preoperative s‐CEA expression.
Formal and Informal Help‐Seeking by Australian Parents who Misuse Alcohol
Authors: Meyer Silke , Eggins Elizabeth
Published: October 2018

Parental substance misuse has a pervasive impact on family functioning, parenting, and, ultimately, child wellbeing and development. Subsequently, linkages with informal and formal support networks are crucial for ameliorating risk. To facilitate engagement with these families prior to identification in child protection systems, it is vital to understand the factors inhibiting and promoting engagement with informal and formal support. This paper examines how different factors influence informal and formal help‐seeking by alcohol‐misusing parents with regard to parenting and family concerns. Parents reporting alcohol problems in a clinical range (n = 322) were drawn from a representative parent sample (n = 1991). Alcohol‐misusing parents reported low help‐seeking for parenting‐focused support services. The findings particularly highlight the role of age, education, socioeconomic status, ethnicity, parenting stress, empowerment and trust in support services for predicting parents' help‐seeking.

‘Examines how different factors influence informal and formal help‐seeking by alcohol‐misusing parents with regard to parenting and family concerns’
Influence of Impregnation and Ion Exchange Sequence on Metal Localization, Acidity and Catalytic Performance of Cobalt BEA Zeolite Catalysts in Fischer‐Tropsch Synthesis
Authors: Flores Camila , Batalha Nuno , Marcilio Nilson R. , Ordomsky Vitaly V. , Khodakov Andrei Y.
Published: October 2018

Cobalt distribution between the external surface and micropores and acidity of the large pore BEA zeolite were controlled by choosing the sequence of impregnation and ion exchange procedures. Higher concentration of ion exchangeable cobalt was observed in the catalyst prepared by ion‐exchange of the zeolite proton form. The presence of Na+ instead of H+ ions in the exchange positions of zeolite favored deposition of cobalt on the external surface. The acid sites in the zeolite micropores can be then restored by subsequent ion exchange of sodium with ammonium nitrate and calcination. The catalytic performance of the cobalt zeolite catalysts prepared using different impregnation and ion exchange procedures was tested in the Fischer‐Tropsch synthesis. Higher reaction rates were observed over the catalysts, which did not contain cobalt ions in the cation sites of the zeolite. Lower methane selectivity, higher selectivity to long chain hydrocarbons and high fraction of isomerized products are observed when cobalt species are located on the zeolite outer surface and acid sites inside the BEA zeolite micropores.
Methanol Promoted Palladium‐Catalyzed Amine Formylation with CO2 and H2 by the Formation of HCOOCH3
Authors: Wang Yanyan , Chen Bingfeng , Liu Shulin , Shen Xiaojun , Li Shaopeng , Yang Youdi , Liu Huizhen , Han Buxing
Published: October 2018

The N‐formylation reaction of amines is one of the most effective measures to make the best use of CO2, since the formamides have widespread applications in industry. Herein, we performed the N‐formylation reaction over Mg−Al layered double hydroxide (Mg−Al LDH) supported Pd catalyst (Pd/LDH) for the first time and studied the relation between the solvent and the mechanism. In this reaction, the methanol can greatly improve the yield of the desired product by forming the HCOOCH3. The catalytic system is effective for various amines including cyclic and alkyl secondary amines. Under the optimized reaction condition, we gained 88.5 %–97.4 % yields of the formamides for various substrates.
Direct Synthesis of H2O2 on Pd Based Catalysts: Modelling the Particle Size Effects and the Promoting Role of Polyvinyl Alcohol
Authors: Giorgianni Gianfranco , Abate Salvatore , Centi Gabriele , Perathoner Siglinda
Published: October 2018

Sol immobilization is a relevant preparation method, particularly for the preparation of Pd‐based catalysts for the direct synthesis of H2O2. In this preparation, polyvinyl alcohol (PVA) acts as capping agent for Pd particles. Modelling the role of PVA on the Pd nanoparticle size and its promoting effect on the selectivity is important to understand better these catalysts. Here, Pd based catalysts prepared by sol immobilization have been tested in a semi‐batch reactor with an H2/O2 ratio ≈1, analysing the influence of the Pd nanoparticle size and the effect of PVA on the rate constants of the reaction network and their change during the reaction. A stepwise testing protocol coupled with transmission electron microscopy characterization as a function of reaction time has been used. These catalysts were compared with other catalysts prepared by hydrazine reduction and impregnation‐decomposition, where PVA is absent. The results are analysed in terms of rate constants for the various rates in the reaction network in relation with the Pd average particle size and related sites distribution, as a function of the changes occurring during extended catalytic tests. The SI‐series of catalysts (prepared by sol‐immobilization) shows enhanced properties, attributed to the effect of PVA capping agent in forming less defective Pd nanoparticles. This induces both a decrease of direct combustion and secondary hydrogenolysis reactions, and an enhancement of the direct synthesis route. The PVA layer limits H2O2 back‐diffusion with a negative influence on the productivity and selectivity, with its removal leading to initial enhanced performances, but in long‐term to a worsening due to sintering of Pd nanoparticles in extended operations.
Investigation of the Isolated Cr(VI) Species in Cr/MCM‐41 Catalysts and its Effect on Catalytic Activity for Dehydrogenation of Propane
Authors: He Dedong , Zhang Yaliu , Yang Shuang , Mei Yi , Luo Yongming
Published: October 2018

Cr‐modified MCM‐41 with different loadings were prepared and tested in the propane dehydrogenation (PDH) reaction. As for Cr/MCM‐41 system, the general knowledge was that high Cr loadings resulted in the reduction of silica surface hydroxyl groups, thus leading to the formation of inactive Cr(III) species, as clusters and/or crystalline Cr2O3. However, in the present work, isolated Cr(VI) states were identified in the Cr/MCM‐41 catalysts, instead of Cr(III) species, using UV‐vis and H2‐TPR. These isolated Cr(VI) species are difficult to reduce, causing the decreased activity for propane conversion and low selectivity towards C3H6 in the PDH process. In contrast, a good dispersion of the Cr species was obtained using a chromium column adsorption process, and the absence of the isolated state of Cr(VI) species on this sample contributed to high activity toward PDH process. The investigation of the isolated Cr(VI) species is very important for the Cr‐based PDH catalyst system.
Performance of methods that separate common and distinct variation in multiple data blocks
Authors: Måge Ingrid , Smilde Age K. , van der Kloet Frans M.
Published: October 2018

In many areas of science, multiple sets of data are collected from the samples. Such data sets can be analyzed by multiblock (or data fusion) methods. The aim is usually to get a holistic understanding of the system or better prediction of some response. Lately, several scientific groups have developed methods for separatingcommonanddistinctvariation between multiple data blocks. Although the objective is the same, the strategies and algorithms are completely different for these methods. In this paper, we investigate the practical properties of the four most popular methods for separating common and distinct variation: JIVE, DISCO, PCA‐GCA, and OnPLS. The main barrier complicating the use of any of these methods is model selection and validation. Especially when the numbers of blocks is more than two. By the use of extensive simulations, we have elucidated the three properties that are important for assessing the validity of the results: The ability to identify the correct model, the ability to estimate the true, underlying subspaces, and the robustness towards misspecification of the model.

The simulated data sets mimic a range of “real life” data, with different dimensionalities and variance structures. We are thus able to identify which methods work best for different types of data structures, and pinpoint weak spots for each method. The results show that PCA‐GCA works best for model selection, while JIVE and DISCO give the best estimates of the subspaces and are most robust towards model misspecification.
Unraveling the Twin and Tunability of the Crystal Domain Sizes in the Medium‐Pore Zeolite ZSM‐57 by Electron Crystallography
Authors: Wang Lei , Yan Nana , Liu Xiaona , Zhao Xuebin , Shen Meikun , Liu Leifeng , Tian Peng , Guo Peng , Liu Zhongmin
Published: October 2018

Tailoring the morphology of a specific crystalline material through distinct crystal growth mechanisms (classical and nonclassical) is challenging. Herein, we report the two unique morphologies of a medium‐pore (10×8‐ring) zeolite, ZSM‐57, prepared by employing an identical organic structure‐directing agent (OSDA) and different inorganic cations, namely Na+ and K+, denoted as ZSM‐57‐Na (pentagonal nanoplates) and ZSM‐57‐K (pentagonal nanoprisms), respectively. The tunable twin domain size and twin boundaries in both samples have been unraveled at the atomic level by electron crystallography. It is of significance to note that the 10‐ring pore openings run perpendicular to the pentagonal nanoplates and nanoprisms. Moreover, the distinct crystal growth mechanisms, which result in the different unique morphologies and tunable twin domains, were further determined by electron crystallography combined with other techniques. Nonclassical growth involving the aggregation of amorphous aluminosilicate nanoparticles to the smooth ZSM‐57‐Na crystal surface dominates the ZSM‐57‐Na crystallization process. For the ZSM‐57‐K sample, the classical layer‐by‐layer growth through the addition of silica molecules to advancing steps on the crystal surface dominates the ZSM‐57‐K crystallization process. The different morphologies of both samples result in the distinct catalytic lifespan of the methanol conversion and selectivity of lower olefins.
A Dimeric 2,9‐Diamino‐1,10‐phenanthroline Derivative Improves Alternative Splicing in Myotonic Dystrophy Type 1 Cell and Mouse Models
Authors: Li Jinxing , Nakamori Masayuki , Matsumoto Jun , Murata Asako , Dohno Chikara , Kiliszek Agnieszka , Taylor Katarzyna , Sobczak Krzysztof , Nakatani Kazuhiko
Published: October 2018

Expanded r(CUG) repeats are the cause of the neurological disorder myotonic dystrophy type 1 (DM1). The pathological features of DM1 include the formation of ribonuclear foci containing expanded r(CUG) repeats, which sequester the MBNL1 protein and lead to the misregulation of alternative pre‐mRNA splicing. Small molecules that bind to the r(CUG) repeats and improve alternative splicing have therapeutic potential in the treatment of DM1. Herein, the synthesis of DDAP (a dimeric form of the CUG‐binding molecule DAP reported previously), its binding properties to r(CUG) repeats, and its effect on the misregulation of splicing are reported. The surface plasmon resonance assay, circular dichroism spectra, and ESI‐TOF mass spectrometry results confirmed the binding of DDAP to r(CUG)9 repeats. Studies on a DM1 cell model and a DM1 mouse model revealed that DDAP was partially effective in the recovery of the pre‐mRNA splicing defects. The mechanism underlying this recovery was studied in vitro through a competitive binding assay, and suggested that DDAP could interfere with the binding of MBNL1 to r(CUG) repeats in a concentration‐dependent manner.
To delay or not to delay, that is the question for patients with acute lymphoblastic leukemia who do not receive prophylactic cranial irradiation
Authors: Pui Ching‐Hon
Published: October 2018

To determine the impact of delaying diagnostic lumbar puncture and initial intrathecal therapy on the treatment outcomes of children with newly diagnosed acute lymphoblastic leukemia treated without prophylactic cranial irradiation, Yeh and colleagues have updated their Taiwan Pediatric Oncology Group Acute Lymphoblastic Leukemia 2002 clinical trial. They have found that this treatment strategy reduces the rate of traumatic lumbar puncture with blasts to zero, and it tends to improve the outcomes of patients with a central nervous system 2 or 3 status according to the event‐free survival, the overall survival, and the cumulative risk of central nervous system relapse in comparison with historical controls.
Continuous‐flow Synthesis of Aryl Aldehydes by Pd‐catalyzed Formylation of Aryl Bromides Using Carbon Monoxide and Hydrogen
Authors: Hone Christopher A. , Lopatka Pavol , Munday Rachel , O'Kearney‐McMullan Anne , Kappe C. Oliver
Published: October 2018

A continuous‐flow protocol utilizing syngas (CO and H2) was developed for the palladium‐catalyzed reductive carbonylation of (hetero)aryl bromides to their corresponding (hetero)aryl aldehydes. The optimization of temperature, pressure, catalyst and ligand loading, and residence time resulted in process‐intensified flow conditions for the transformation. In addition, a key benefit of investigating the reaction in flow is the ability to precisely control the CO‐to‐H2 stoichiometric ratio, which was identified as having a critical influence on yield. The protocol proceeds with low catalyst and ligand loadings: palladium acetate (1 mol % or below) and cataCXium A (3 mol % or below). A variety of (hetero)aryl bromides at a 3 mmol scale were converted to their corresponding (hetero)aryl aldehydes at 12 bar pressure (CO/H2=1:3) and 120 °C reaction temperature within 45 min residence time to afford products mostly in good‐to‐excellent yields (17 examples). In particular, a successful scale‐up was achieved over 415 min operation time for the reductive carbonylation of 2‐bromo‐6‐methoxynaphthalene to synthesize 3.8 g of 6‐methoxy‐2‐naphthaldehyde in 85 % isolated yield. Studies were conducted to understand catalyst decomposition within the reactor by using inductively coupled plasma–mass spectrometry (ICP–MS) analysis. The palladium could easily be recovered using an aqueous nitric acid wash post reaction. Mechanistic aspects and the scope of the transformation are discussed.
Nerves and Proliferation of Progenitor Cells in Limb Regeneration
Authors: Stocum David L.
Published: October 2018

Nerves, in conjunction with the apical epidermal cap (AEC), play an important role in the proliferation of the mesenchymal progenitor cells comprising the blastema of regenerating urodele amphibian limbs. Reinnervation after amputation requires factors supplied by the forming blastema, and neurotrophic factors must be present at or above a quantitative threshold for mitosis of the blastema cells. The AEC forms independently of nerves, but requires nerves to be maintained. Urodele limb buds are independent of nerves for regeneration, but innervation imposes a regenerative requirement for nerve factors on their cells as they differentiate. There are three main ideas on the functional relationship between nerves, AEC, and blastema cells: (1) nerves and AEC produce factors with different roles in maintaining progenitor status and mitosis; (2) the AEC produces the factors that promote blastema cell mitosis, but requires nerves to express them; (3) blastema cells, nerves, and AEC all produce the same factor(s) that additively attain the required threshold for mitosis.
Phrenic nerve stimulation to treat patients with central sleep apnoea and heart failure
Authors: Costanzo Maria Rosa , Ponikowski Piotr , Coats Andrew , Javaheri Shahrokh , Augostini Ralph , Goldberg Lee R. , Holcomb Richard , Kao Andrew , Khayat Rami N. , Oldenburg Olaf , Stellbrink Christoph , McKane Scott , Abraham William T. ,   for the remedē System Pivotal Trial Study Group
Published: October 2018

Aims

The presence of central sleep apnoea (CSA) is associated with poor prognosis in patients with heart failure (HF). The aim of this analysis was to evaluate if using phrenic nerve stimulation to treat CSA in patients with CSA and HF was associated with changes in HF‐specific metrics.

Methods and results

All patients randomized in the remedē System Pivotal Trial and identified at baseline with HF were included (n = 96). Effectiveness data from treatment and former control groups were pooled based on months since therapy activation. Changes from baseline to 6 and 12 months in sleep metrics, Epworth Sleepiness Scale, patient global assessment health‐related quality of life, Minnesota Living with Heart Failure Questionnaire (MLHFQ), and echocardiographic parameters are reported. HF hospitalization, cardiovascular death, and the composite of HF hospitalization or cardiovascular death within 6 months are reported by the original randomized group assignment for safety assessment. Sleep metrics and quality of life improved from baseline to 6 and 12 months. At 12 months, MLHFQ scores changed by –6.8 ± 20.0 (P = 0.005). The 6‐month rate of HF hospitalization was 4.7% in treatment patients (standard error = 3.3) and 17.0% in control patients (standard error = 5.5) (P = 0.065). Reported adverse events were as expected for a transvenous implantable system.

Conclusions

Phrenic nerve stimulation reduces CSA severity in patients with HF. In parallel, this CSA treatment was associated with benefits on HF quality of life.
One Step Up in Antiproliferative Activity: The Ru‐Zn Complex [RuCp(PPh3)2‐µ‐dmoPTA‐1κP:2κ2N,N′‐ZnCl2](CF3SO3)
Authors: Mendoza Zenaida , Lorenzo‐Luis Pablo , Scalambra Franco , Padrón José M. , Romerosa Antonio
Published: October 2018

The synthesis, characterization and antiproliferative activity of the bimetallic Ru‐Zn complex [RuCp(PPh3)2‐µ‐dmoPTA‐1κP:2κ2N,N′‐ZnCl2](CF3SO3) (4) and the monometallic Ru complex [RuCp(PPh3)2(dmoPTA‐1κP)](CF3SO3) (5) are presented. Against human lung, cervix, breast, and colon solid tumor cell lines, complex 4 showed an enhanced antiproliferative activity (GI50 = 30–83 nm) when compared to its parent complex [RuCp(PPh3)2(HdmoPTA‐1κP)](CF3SO3) (2). Additionally, it was significantly more active against the breast cancer cell line T‐47D than its sibling cobalt complex [RuCp(PPh3)2‐µ‐dmoPTA‐1κP:2κ2N,N′‐CoCl2](CF3SO3) (3). When evaluated against non‐tumor human cell line BJ‐hTert, complex 4 was 3–8 times less active, indicating a large selectivity for tumor cells, while compound 5 was not selective.
Copper Sulfides: Earth‐Abundant and Low‐Cost Thermoelectric Materials
Authors: Mulla Rafiq , Rabinal Mohammad Hussain Kasim
Published: October 2018

The depletion of nonrenewable energy sources insisted the search for new types of energy solutions. Thermoelectric conversion is one possible energy solution which converts waste heat into useful electricity. In the past several years, thermoelectric research developed many novel materials. Among these, most of the practically useful materials with better performance are based on Bi, Pb, Te, and Sb, but are toxic and expensive. There is a need of earth‐abundant, low‐cost, and less‐toxic compounds with superior thermoelectric performance so as to realize the large‐scale commercial applications. Recent studies have identified eco‐friendly thermoelectric materials based on the alloys of copper and sulfur, suggesting an alternative to the well‐established expensive thermoelectric materials. These compounds exhibit interesting electronic properties with better thermoelectric efficiency (zT). The structural properties permit to decouple electrical and thermal conductivities, which is an essential requirement to get improved efficiency. Several approaches, such as phase tuning, doping, nanostructure/microstructure designing, compound formation, etc., are chosen to increase the performance. On the whole, the present review summarizes the strategies and techniques that have been adopted to improve the thermoelectric behavior of copper sulfides and its compounds.
From the Change of the Pattern to the Change in the Pattern. The Trilateral Game in the Italian Intergovernmental Relations
Authors: Bolgherini Silvia , Di Giulio Marco , Lippi Andrea
Published: October 2018

Studies on federalism, regionalism and devolution often tackle the processes of institutional change in a country's polity merely as transitions from an institutional pattern to another, thus mainly focusing on the role of legal frameworks and Constitutional setting in the transition from an equilibrium to another. Such an approach overlooks the role of incremental dynamics: what happens after a new constitutional equilibrium has been reached? Does it stand still, crystallized by formal institutions, or does it evolve in time? This article illustrates the relevance of incremental institutional changes that occur after a major Constitutional reform and shows how an alteration in the distribution of resources among actors may heavily affect the territorial arrangement and the intergovernmental relations (IGRs) of a country. It focuses on the Italian case and the change in its IGRs between 2001 and 2016. Through a secondary analysis, a scrutiny of the trilateral game among the State, the Regions and the Local Authorities – played by reshaping and implementing the initial arrangement through gradual, piecemeal and layered modifications – will be conducted. Evidence is displayed through Dente (1997) resources (legal, political, financial and cognitive) framework. The main finding is that the change in the pattern turns out to be less visible, sometimes ambiguous and sticky, and more uncertain than a change of the pattern, but equally deep and effective. In the conclusion, some interpretative hypotheses for further research on the relevance of change in the pattern and its generalization for multi‐level system countries are proposed.
From cellular morphology to molecular and epigenetic anomalies of myelodysplastic syndromes
Authors: Gadji Macoura , Pozzo Aline Rangel
Published: October 2018

Myelodysplastic syndromes (MDSs) are a myeloid neoplasm with a propensity for natural evolution or transformation to acute leukemias (AL) over time. Mechanisms for MDS transformation to AL remain poorly understood but are related to genomic instability, which affects the production of the different cell lineages. Genomic instability is also generated by dysfunctional telomeres. Indeed telomeres, the protective ends of chromosomes are the backbone of genome stability. Nuclear telomere remodeling is an early indicator of nuclear remodeling preceding the onset of genomic instability and MDS. This review aims to revisit the pathogenesis and pathophysiology of MDS from morphology and cytogenetics to molecular and epigenetic mechanisms. Furthermore, this review will highlight and discuss recent breakthroughs in dysfunctional telomeres and nuclear telomere architecture roles in the pathogenesis and physiopathology of MDS in the global context of genomic instability.
Overlapping clustering of gene expression data using penalized weighted normalized cut
Authors: Teran Hidalgo Sebastian J. , Zhu Tingyu , Wu Mengyun , Ma Shuangge
Published: October 2018

Clustering has been widely conducted in the analysis of gene expression data. For complex diseases, it has played an important role in identifying unknown functions of genes, serving as the basis of other analysis, and others. A common limitation of most existing clustering approaches is to assume that genes are separated into disjoint clusters. As genes often have multiple functions and thus can belong to more than one functional cluster, the disjoint clustering results can be unsatisfactory. In addition, due to the small sample sizes of genetic profiling studies and other factors, there may not be sufficient evidence to confirm the specific functions of some genes and cluster them definitively into disjoint clusters. In this study, we develop an effective overlapping clustering approach, which takes account into the multiplicity of gene functions and lack of certainty in practical analysis. A penalized weighted normalized cut (PWNCut) criterion is proposed based on the NCut technique and an norm constraint. It outperforms multiple competitors in simulation. The analysis of the cancer genome atlas (TCGA) data on breast cancer and cervical cancer leads to biologically sensible findings which differ from those using the alternatives. To facilitate implementation, we develop the function
pwncut in the
R package
NCutYX.
Explaining steam‐enhanced carbonation of CaO based on first principles
Authors: Yang Peng , Duan Lunbo , Tang Hongjian , Cai Tianyi , Sun Zhao
Published: October 2018

Calcium‐based sorbents have been regarded as effective agents for capturing CO2 from industrial flue gas. Recent studies have shown that steam can enhance the carbonation performance of calcium‐based sorbents. In this paper, a CaO (001) surface was made to investigate the micro‐level mechanism of steam‐enhanced carbonation based on first principles calculations. Charge transfer and bond population were calculated to evaluate an interaction effect between adsorbates and the CaO (001) surface. Individual adsorption of CO2 and H2O was compared with binary adsorption and co‐adsorption of the two molecules on the CaO (001) surface, based on dispersion‐corrected density functional theory (DFT‐D) calculations. First, the predicted adsorption energies suggest the O‐top site is the best site. It forms carbonate‐like structure and hydroxyl‐like structure for the individual adsorption of CO2 and H2O. Binary adsorption calculations indicate that H2O is more easily adsorbed by the CaO (001) surface than CO2. The adsorption of H2O and CO2 adsorption are promoted in comparison with their individual adsorption on the CaO (001) surface. Moreover, the analysis of adsorption energies and partial density of states (PDOS) suggests that a H2O‐CaO (001) surface (CaO (001) surface that has already adsorbed H2O) is more reactive than the clean CaO (001) surface for CO2 adsorption, which further supports the idea that the steam‐enhanced mechanism is an Eley–Rideal (E–R) mechanism, which means H2O is adsorbed on the CaO surface, and then CO2 is adsorbed. © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd.