bluuebunny/crossref_metadata_2025 huggingface dataset:
Reconstruction of precipitation δ18O over the Tibetan Plateau since 1910
Authors: Gao Jing , Shen Samuel S. P. , Yao Tandong , Tafolla Nancy , Risi Camille , He You
Published: May 2015

An accurate representation of the spatiotemporal variation of stable isotopes in precipitation over the Tibetan Plateau (TP) is critical information for hydrological and ecological applications for the region. This paper reconstructs annual δ18O data with 2.5° × 3.75° latitude‐longitude resolutions over the TP since 1910 using the spectral optimal gridding (SOG) method. The SOG calculates empirical orthogonal functions (EOFs) from the Laboratoire de Météorologie Dynamique isotopic version general circulation model over the TP from 1978 to 2007 and regresses the δ18O data of 10 ice cores over TP against the EOF basis functions. The reconstructed data can effectively demonstrate spatiotemporal characteristics of TP precipitation δ18O. The spatial average interannual δ18O anomalies agree well with the time series of Guliya ice core δ18O, implying Guliya δ18O's typical representation of the TP δ18O temporal variation.
Volume Measurement
Authors: Davis Thomas , Zanella Andrew
Published: May 2015

This unit describes the common types of volumetric apparatus used in the life science laboratory, their use, and care. When an experimenter needs to prepare solutions at accurate concentrations and quantitatively transfer samples of liquid from one container to another, an array of glassware and plasticware is available for these operations ranging from a microliter to more than a liter in volume. Considerations of temperature, solvent compatibility, and safety also need to be taken into account. © 2015 by John Wiley & Sons, Inc.
Fluorescence Spectroscopy
Authors: Lee Claudia Y.
Published: May 2015

Fluorescence is an extremely powerful tool in modern biology, physics, and chemistry laboratories. This unit begins with the physics of fluorescence, the biological applications of fluorescence, and the mechanisms behind spectrometers and fluorometers, followed by strategies to choose an appropriate fluorophore according to the instrumentation at hand. The first part of the unit walks the reader through the acquisition of an absorption spectrum and explains how it can be used to measure the degree of labeling on conjugated proteins. The discussion then extends into how to obtain fluorescence emission spectra, which can be utilized as fluorescence indicators for protein detection. © 2015 by John Wiley & Sons, Inc.
Agarose Gel Electrophoresis
Authors: Armstrong Jennifer A. , Schulz Joseph R.
Published: May 2015

Agarose gel electrophoresis, which separates and sizes linear DNA and RNA fragments, is arguably the most basic and essential technique in molecular biology. It is commonly employed for analysis of PCR products, plasmid DNA, and products of restriction enzyme digestion. It is the first step for analysis of specific DNA and RNA fragments by northern and Southern blots. In this unit, we provide both written instructions and photographic images to take the reader from preparing a first agarose gel to analyzing results and determining the size of sample DNA. We include two protocols: agarose gel electrophoresis (commonly used to analyze DNA) and denaturing gel electrophoresis (for analyzing RNA). We have divided each protocol into four basic steps: (1) preparing and pouring the agarose gel; (2) preparing and loading samples; (3) running the agarose gel; and (4) staining the gel using the fluorescent stain ethidium bromide to visualize DNA and RNA. © 2015 by John Wiley & Sons, Inc.
Neural Crest Cells from Dual SMAD Inhibition
Authors: Fattahi Faranak , Studer Lorenz , Tomishima Mark J.
Published: May 2015

Neural crest (NC) cells are migratory multipotent progenitors that delaminate from the neural tube during embryonic development and give rise to various cell types in different organs. These cells are a transient embryonic cell population and therefore difficult to obtain from primary sources. Deriving NC from human pluripotent stem cells offers an alternative way to provide large‐scale human NC cells for developmental and disease‐related studies. In recent years, the protocols to make these cells have matured, incorporating the efficient conversion of pluripotent stem cells to neural cells through dual SMAD inhibition and early Wnt activation to increase the yield of NC cells. Here, we provide a minor variation to this NC protocol that has been successful for many in our laboratories. © 2015 by John Wiley & Sons, Inc.
Fluorescently Labeled Human Papillomavirus Pseudovirions for Use in Virus Entry Experiments
Authors: Samperio Ventayol Pilar , Schelhaas Mario
Published: May 2015

Human papillomaviruses (HPV) infect skin or mucosal epidermis. The simplistic capsid consists of a major capsid protein L1, a minor capsid protein L2, and a double‐stranded circular DNA of about 8kB in size. The development of HPV‐based vectors [i.e., pseudovirions (PsV)] as tools to study the initial infection has facilitated our understanding of HPV entry. The covalent coupling of fluorescent molecules to these PsV allows following the viruses en route to the nucleus, i.e., the site of replication. In the first section, we describe a facile method to covalently label HPV PsV that retain their infectivity. In this method, fluorophores coupled to a reactive succinimidyl ester are covalently attached to amine residues in the virion in a one‐step chemical reaction. In the second section of this unit, several assays are outlined that use the fluorescently labeled virions for entry studies in live and fixed cells. © 2015 by John Wiley & Sons, Inc.
Rotaviruses: Extraction and Isolation of RNA, Reassortant Strains, and NSP4 Protein
Authors: Yakshe Krystle A. , Franklin Zachary D. , Ball Judith M.
Published: May 2015

Rotavirus (RV) contains 11 double‐stranded RNA segments that encode for twelve structural and nonstructural proteins. The separation and isolation of viral RNA is a necessary precursor for many experimental techniques and can be useful for rapid RV RNA typing and sequencing of different rotavirus strains. The segmented genome enables RV to recombine easily. These recombinant viruses are essential for many purposes, including generation of potential vaccine strains. Rotavirus gene 10 expresses the viral enterotoxin, NSP4, which has been the focus of several studies due to the influence of NSP4 on rotavirus replication, morphogenesis, and pathogenesis. This unit will describe the isolation and separation of viral RNAs, the production characterization of recombinant RV in culture, and the expression and isolation of NSP4 in mammalian and insect cells. © 2015 by John Wiley & Sons, Inc.
The Development and Application of Sulfur Dioxide Surrogates in Synthetic Organic Chemistry
Authors: Emmett Edward J. , Willis Michael C.
Published: May 2015

Sulfur dioxide has a rich and varied chemistry that can be traced back to the early 1900s. Despite the potential utility of sulfur dioxide based reactions, delivering products such as sulfones, sulfonamides and sulfinic acids, the number of examples of these reactions being exploited in synthesis is arguably lower than would be expected. One significant contributing factor to this is undoubtedly the toxic and gaseous nature of SO2. One strategy to overcome this limitation is to employ an equivalent, or surrogate, so that the gaseous reagent is no longer needed. This strategy has proven to be a success, with a number of methods being described. The reactions reported include variants of traditional reactions in which the gaseous reagent has been replaced with a surrogate, and also new transformations for which no gaseous reaction is known. This Focus Review discusses the origin of sulfur dioxide surrogates and then considers their application to synthetic organic chemistry.
Comparative Analysis of the Reactivity of Diazirine‐Based Photoaffinity Probes toward a Carbohydrate‐Binding Protein
Authors: Sakurai Kaori , Yasui Tomoki , Mizuno Sakae
Published: May 2015

A set of lactose‐based photoaffinity probes bearing either alkyl diazirine or trifluoromethylphenyl diazirine (TPD) groups were designed and synthesized to directly compare their efficiency in photocrosslinking a carbohydrate‐binding protein. The crosslinking efficiency of the TPD probes was higher than the alkyl diazirine probes when reacted with a single binding protein. However, the alkyl diazirine probe with a small alkyne tag achieved more selective photoaffinity labeling of a binding protein in cell lysate than the corresponding TPD probe.
Chiral Lithium Binaphtholate for Enantioselective Michael Addition of Acyclic α‐Alkyl‐β‐Keto Esters to Vinyl Ketones
Authors: Kotani Shunsuke , Moritani Miyuki , Nakajima Makoto
Published: May 2015

Asymmetric Michael addition of acyclic α‐alkyl‐β‐keto esters with vinyl ketones catalyzed by a chiral lithium binaphtholate is described. Lithium binaphtholates, prepared from BINOL derivatives and inexpensive LiOH, effectively promoted the transformation of acyclic α‐alkyl‐β‐keto esters in a highly enantioselective manner, affording Michael adducts bearing chiral quaternary carbon centers.
Effectiveness of glatiramer acetate compared to other multiple sclerosis therapies
Authors: Izquierdo Guillermo , García‐Agua Soler Nuria , Rus Macarena , García‐Ruiz Antonio José
Published: May 2015

Objective

To assess the effectiveness of glatiramer acetate (GA) compared to other multiple sclerosis (MS) therapies in routine clinical practice.

Materials and methods

Observational cohort study carried out in MS patients treated with GA (GA cohort) or other MS therapies –switched from GA– (non‐GA cohort). Study data were obtained through review of our MS patient database. The primary endpoint was the Expanded Disability Status Scale (EDSS) scores reached at the end of treatment/last check‐up.

Results

A total of 180 patients were included: GA cohort n = 120, non‐GA cohort n = 60. Patients in the GA cohort showed better EDSS scores at the end of treatment/last check‐up (mean ± SD, 2.8 ± 1.8 vs. 3.9 ± 2.2; P = 0.001) and were 1.65 times more likely to show better EDSS scores compared to the non‐GA cohort (odds ratio, 0.606; 95%CI, 0.436–0.843; P = 0.003). Patients in the GA cohort showed longer mean time to reach EDSS scores of 6 (209.1 [95%CI, 187.6–230.6] vs. 164.3 [95%CI, 137.0–191.6] months; P = 0.004) and slower disability progression (hazard ratio, 0.415 [95%CI, 0.286–0.603]; P < 0.001). The annualized relapse rate was lower in the GA cohort (mean ± SD, 0.5 ± 0.5 vs. 0.8 ± 0.5; P = 0.001) and patients’ quality of life was improved in this study cohort compared to the non‐GA cohort (mean ± SD, 0.7 ± 0.1 vs. 0.6 ± 0.2; P = 0.01).

Conclusions

GA may slow down the progression of EDSS scores to a greater extent than other MS therapies, as well as achieving a greater reduction in relapses and a greater improvement in patients’ quality of life. Switching from GA to other MS therapies has not proved to entail a better response to treatment.
Rightward dominance in temporal high‐frequency electrical asymmetry corresponds to higher resting heart rate and lower baroreflex sensitivity in a heterogeneous population
Authors: Tegeler Charles H. , Shaltout Hossam A. , Tegeler Catherine L. , Gerdes Lee , Lee Sung W.
Published: May 2015

Objective

Explore potential use of a temporal lobe electrical asymmetry score to discriminate between sympathetic and parasympathetic tendencies in autonomic cardiovascular regulation.

Methods

131 individuals (82 women, mean age 43.1, range 13–83) with diverse clinical conditions completed inventories for depressive (CES‐D or BDI‐II) and insomnia‐related (ISI) symptomatology, and underwent five‐minute recordings of heart rate and blood pressure, allowing calculation of heart rate variability and baroreflex sensitivity (BRS), followed by one‐minute, two‐channel, eyes‐closed scalp recordings of brain electrical activity. A temporal lobe high‐frequency (23–36 Hz) electrical asymmetry score was calculated for each subject by subtracting the average amplitude in the left temporal region from amplitude in the right temporal region, and dividing by the lesser of the two.

Results

Depressive and insomnia‐related symptomatology exceeding clinical threshold levels were reported by 48% and 50% of subjects, respectively. Using a cutoff value of 5% or greater to define temporal high‐frequency asymmetry, subjects with leftward compared to rightward asymmetry were more likely to report use of a sedative‐hypnotic medication (42% vs. 22%, P = 0.02). Among subjects with asymmetry of 5% or greater to 30% or greater, those with rightward compared to leftward temporal high‐frequency asymmetry had higher resting heart rate (≥5% asymmetry, 72.3 vs. 63.8, P = 0.004; ≥10%, 71.5 vs. 63.0, P = 0.01; ≥20%, 72.2 vs. 64.2, P = 0.05; ≥30%, 71.4 vs. 64.6, P = 0.05). Subjects with larger degrees of rightward compared to leftward temporal high‐frequency asymmetry had lower baroreflex sensitivity (≥40% asymmetry, 10.6 vs. 16.4, P = 0.03; ≥50% asymmetry, 10.4 vs. 16.7, P = 0.05).

Conclusion

In a heterogeneous population, individuals with rightward compared to leftward temporal high‐frequency electrical asymmetry had higher resting heart rate and lower BRS. Two‐channel recording of brain electrical activity from bilateral temporal regions appears to hold promise for further investigation as a means to assess cortical activity associated with autonomic cardiovascular regulation.
Efficient and Flexible Supercapacitors Assembled on Metal Spikes
Authors: Fan Xing , Fan Zongbo , Peng Ming , Cheng Li , Du Jun , Zou Dechun , Tao Changyuan
Published: May 2015

Lavender‐like, lightweight, and flexible supercapacitive electrodes with high specific capacitance have been fabricated for the first time by assembling petal‐like nano‐nickel oxides on nickel spikes that are grown by using a simple non‐templated method. Compared with traditional fiber‐shaped electrodes, the specific capacitance of these electrodes increases six‐fold to 4.47 F cm−2. For a 1 cm‐long spike electrode, the capacitance reaches over 1.4 F, and no evident drop is observed at a bending angle of 180°. Both the mechanical strength and large current discharging property are unexpectedly good. The spike structure makes the apparent mass density of the electrode as light as carbon fiber, and exhibits considerable potential for use in future portable energy‐storage devices.
Catalytic effect of MgCl2 on cotton stalk pyrolysis for chemical production at low temperature
Authors: Liu Xinliang , Dong Yan , Yin Hailiang , Zhang Guicai
Published: May 2015

Cotton stalk pyrolysis catalyzed by magnesium chloride was carried out in a fixed bed reactor in a temperature range of 493–553 K. The feedstock characteristics, product distribution, pyrolysis oil composition, and solid residue composition were analyzed. The presence of MgCl2 significantly changed the product distribution of the pyrolysis oil and oils with only two targeted chemicals successfully collected for the purpose of chemical production. The effects of catalyst loading and pyrolysis temperature on pyrolysis behaviour for the furfural and acetic acid production were studied systematically. The furfural and acetic acid concentration in pyrolysis oil increased in the presence of magnesium chloride in our investigated temperature range. The furfural and acetic acid contents in water‐free pyrolysis oil are about 54 % and 28 % when the pyrolysis temperature is 553 K. The results of solid product analysis showed that 85 % of hemicellulose was decomposed, while cellulose and lignin were relatively stable. This study makes it possible to produce chemicals from biomass material through a multi‐step pyrolysis process.
Insights on the UV/Vis, Fluorescence, and Cyclic Voltammetry Properties and the Molecular Structures of ZnII Tetraphenylporphyrin Complexes with Pseudohalide Axial Azido, Cyanato‐N, Thiocyanato‐N, and Cyanido Ligands
Authors: Denden Zouhour , Ezzayani Khaireddine , Saint‐Aman Eric , Loiseau Frédérique , Najmudin Shabir , Bonifácio Cecilia , Daran Jean‐Claude , Nasri Habib
Published: May 2015

The syntheses, spectroscopic and photophysical properties, and molecular structures of azido‐ (1), cyanato‐N‐ (2), thiocyanato‐N‐ (3), and cyanido‐ (4) (meso‐tetraphenylporphyrinato)zinc(II) complexes are reported. These species were prepared by using cryptand‐222 to solubilize the pseudohalide salts in organic solvents. The UV/Vis spectra of these zinc metalloporphyrins are solvent‐dependent and exhibit large redshifted Soret bands compared with those of the [Zn(Porph)L] derivatives in which Porph is a meso‐porphyrinato ligand and L is a monodentate neutral axial ligand. The room‐temperature fluorescence spectra of the zinc complexes 1–4 indicate that the Q bands are not very affected by the nature of the axial ligands, and their positions are very close to those of previously reported (meso‐porphyrinato)zinc complexes. The quantum yields of the S1 → So fluorescence of 1–4 range between 2.8 and 5.5 %, and their fluorescence lifetimes are the same (1.7 ns). Cyclic voltammetry investigations on 1–4 show that the characteristic potentials for the reduction and the two first oxidations of the porphyrin ring are not very affected by the nature of the axial ligand. A third irreversible oxidation of the porphyrin ring is observed. Additional anodic irreversible waves are observed for the thiocyanato‐N (3) and cyanido (4) species. The solid‐state molecular structures of 1–4 are the first examples of zinc porphyrin complexes with anionic ligands. The average equatorial zinc–pyrrole N atom (Zn–Np) distances for 1–4 range between 2.083(1) and 2.117(2) Å and are much longer than those of the related pentacoordinate zinc porphyrin complexes with monodentate neutral ligands. As a consequence, the displacement of the Zn2+ cation from the mean 24‐atom plan of the porphyrin core is significant (ca. 0.5 Å), and the porphyrin core is very distorted. The crystal structures of 1–4 are stabilized by weak intermolecular π interactions, C–H···Cg (Cg are the centroids of some six‐membered phenyl rings and five‐membered pyrrole rings). The molecular structure of 1 is further stabilized by weak intermolecular C–H···N hydrogen bonds between one carbon atom of cryptand‐222 and the terminal nitrogen atom of the azido ligand.
Synthesis of Chiral (Indol‐2‐yl)methanamines and Insight into the Stereochemistry Protecting Effects of the 9‐Phenyl‐9‐fluorenyl Protecting Group
Authors: Lood Christopher S. , Laine Aino E. , Högnäsbacka Antonia , Nieger Martin , Koskinen Ari M. P.
Published: May 2015

Tetrahydro‐β‐carbolines, a privileged structural feature in natural products and pharmaceutically active compounds, has been the cause for considerable research interest, spanning many decades. Herein is reported the synthesis of the structurally closely related compounds denoted as (indol‐2‐yl)methanamines, in 99 % ee using amino acid starting materials, coupled with a 9‐phenyl‐9‐fluorenyl (Pf) protecting group strategy. Furthermore a conformational study of Pf‐protected α‐amino carbonyl compounds were undertaken by means of DFT refined molecular mechanics calculation, X‐ray crystallography measurements and NMR experiments in order to elucidate the stereochemical protecting properties induced by the Pf group.
Efficacy and safety of nicoboxil/nonivamide ointment for the treatment of acute pain in the low back – A randomized, controlled trial
Authors: Gaubitz M. , Schiffer T. , Holm C. , Richter E. , Pisternick‐Ruf W. , Weiser T.
Published: May 2015

Background

Until now, nonivamide/nicoboxil ointment has not been tested in a randomized trial for the treatment of acute non‐specific low back pain.

Methods

This phase III randomized, double‐blind, active‐ and placebo‐controlled, multi‐centre trial investigated efficacy, safety and tolerability of topical nicoboxil 2.5%/nonivamide 0.4% for treatment of acute non‐specific low back pain [primary endpoint: pain intensity (PI) difference between pre‐dose baseline and 8 h after the first application].

Results

Patients (n = 805), 18–74 years of age were treated for up to 4 days with nicoboxil 2.5%/nonivamide 0.4%, nicoboxil 2.5%, nonivamide 0.4% or placebo ointment. Pre‐dose baseline pain intensity (6.6 on a 0‐ to 10‐point numerical rating scale) was reduced by 1.049 points with placebo, by 1.428 points with nicoboxil, by 2.252 points with nonivamide and by 2.410 points with nicoboxil/nonivamide after 8 h (p < 0.0001 for nicoboxil/nonivamide vs. placebo, nicoboxil; p = 0.4171 for nicoboxil/nonivamide vs. nonivamide). At the end of treatment, the combination provided more pronounced PI reduction (3.540 points) compared with nicoboxil (2.371, p < 0.0001), nonivamide (3.074, p = 0.0259) and placebo (1.884, p < 0.0001). Low back mobility scores on Day 1 were better for the combination compared with all other treatments (p < 0.044); on Day 2–4, scores were better than for placebo and nicoboxil (p < 0.003). Patients assessed efficacy of the combination as greater than of the comparators (p ≤ 0.0129). All treatments were tolerated well. No treatment‐related serious adverse events were reported.

Conclusion

Nicoboxil/nonivamide ointment is an effective, well‐tolerated medication for the treatment of acute non‐specific low back pain.
Optically Transparent Electrodes Modified with Sulfide Ion‐Covered CdS Quantum Dots for Sensitive Photoelectrochemical Detection of Sulfhydryl‐Containing Compounds
Authors: Zhang Lin , Hao Yuanqiang , Wang Xiaoying , Long Yunfei , Ramos Angela , Jiang Dianlu , Ma Xiaohua , Lin Qinlu , Zhou Feimeng
Published: May 2015

A sensitive and selective photoelectrochemical sensor has been developed. Negatively charged, citrate‐capped CdS quantum dots (QDs) are assembled layer‐by‐layer onto indium tin oxide (ITO) electrodes precoated with positively charged poly(diallyldimethylammonium chloride). By exposing the modified photoelectrochemical electrodes to a Na2S solution, QDs can be covered with excess S2− ions. The weakly bound S2− ions are easily replaceable with a sulphydryl‐containing analyte, and the photocurrent decrease is proportional to the analyte concentration. The detection limit is 0.4 nM for cysteine with a linear range of 1.0–100.0 nM. The level of cysteine in human serum samples has been quantified.
Outdoor Performance and Stability under Elevated Temperatures and Long‐Term Light Soaking of Triple‐Layer Mesoporous Perovskite Photovoltaics
Authors: Li Xiong , Tschumi Manuel , Han Hongwei , Babkair Saeed Salem , Alzubaydi Raysah Ali , Ansari Azhar Ahmad , Habib Sami S. , Nazeeruddin Mohammad Khaja , Zakeeruddin Shaik M. , Grätzel Michael
Published: May 2015

Lack of proven stability has become a major obstacle on the path of metal halide perovskite solar cells (PSCs), in particular methylammonium lead triiodide (MAPbI3), towards commercial viability. This correlates with the intrinsic affinity of MAPbI3 towards moisture and ambient air in particular, leading to its degradation in ambient conditions. We performed extensive stability tests to prove the durability of hole‐conductor‐free PSCs based on a triple‐layer architecture employing carbon as a back contact, including outdoor tests in the hot desert climate and indoor long‐term light soaking as well as heat exposure during 3 months at 80–85 °C. These results show no evidence for device degradation under the test conditions, confirming that the triple‐layer device architecture provides a promising path towards realizing efficient and stable perovskite photovoltaics.
Tissue concentrations as the dose metric to assess potential toxic effects of metals in field-collected fish: Copper and cadmium
Authors: Meador James P.
Published: May 2015

The present study examined the available literature linking whole-body tissue concentrations with toxic effects in fish species for copper and cadmium. The variability in effect concentration for both copper and cadmium among species occurred within an order of magnitude for all responses, whereas the range for lethal toxicity based on water exposure spanned approximately 4 to 5 orders of magnitude. Fish tissue concentrations causing adverse effects were just above background concentrations, occurring between 1 μg/g and 10 μg/g for copper and 0.1 μg/g to 4 μg/g for cadmium. The results also show that salmonids are especially sensitive to cadmium, which appears to be a function of chemical potency. No studies were found that indicated adverse effects without increases in whole-body concentration of these metals. This narrow range for dose-response implies that a toxicological spillover point occurs when the detoxification capacity of various tissues within the animal are exceeded, and this likely occurs at a similar whole-body concentration for all naïvely exposed fish species. Elevated whole-body concentrations in fish from the field may be indicative of possible acclimation to metals that may or may not result in effects for target species. Acclimation concentrations may be useful in that they signal excessive metal concentrations in water, sediment, or prey species for a given site and indicate likely toxic effects for species unable to acclimate to excess metal exposure. Using tissue residues as the dose metric for these metals provides another line of evidence for assessing impaired ecosystems and greater confidence that hazard concentrations are protective for all fish species. Environ Toxicol Chem 2015;34:1309–1319. Published 2015 SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.
How do Hospitals Respond to Price Changes? Evidence from Norway
Authors: Januleviciute Jurgita , Askildsen Jan Erik , Kaarboe Oddvar , Siciliani Luigi , Sutton Matt
Published: May 2015

Many publicly funded health systems use activity‐based financing to increase hospital production and efficiency. The aim of this study is to investigate whether price changes for different treatments affect the number of patients treated and the mix of activity provided by hospitals. We exploit the variations in prices created by the changes in the national average treatment cost per diagnosis‐related group (DRG) offered to Norwegian hospitals over a period of 5 years (2003–2007). We use the data from Norwegian Patient Register, containing individual‐level information on age, gender, type of treatment, diagnosis, number of co‐morbidities and the national average treatment costs per DRG. We employ fixed‐effect models to examine the changes in the number of patients treated within the DRGs over time. The results suggest that a 10% increase in price leads to about 0.8–1.3% increase in the number of patients treated for DRGs, which are medical (for both emergency and elective patients). In contrast, we find no price effect for DRGs that are surgical (for both emergency and elective patients). Moreover, we find evidence of upcoding. A 10% increase in the ratio of prices between patients with and without complications increases the proportion of patients coded with complications by 0.3–0.4 percentage points. Copyright © 2015 John Wiley & Sons, Ltd.
In silico Support for Eschenmoser’s Glyoxylate Scenario
Authors: Andersen Jakob L. , Flamm Christoph , Merkle Daniel , Stadler Peter F.
Published: May 2015

A core topic of research in prebiotic chemistry is the search for plausible synthetic routes that connect the building blocks of modern life, such as sugars, nucleotides, amino acids, and lipids to “molecular food sources” that were likely to have been abundant on early Earth. In a recent contribution, Albert Eschenmoser emphasised the importance of catalytic and autocatalytic cycles in establishing such abiotic synthesis pathways. The accumulation of intermediate products furthermore provides additional catalysts that allow pathways to change over time. We show here that generative models of chemical spaces based on graph grammars make it possible to study such phenomena in a systematic manner. In addition to reproducing the key steps of Eschenmoser’s hypothesis paper, we discovered previously unexplored potentially autocatalytic pathways from HCN to glyoxylate. A cascade of autocatalytic cycles could efficiently re‐route matter, distributed over the combinatorial complex network of HCN hydrolysation chemistry, towards a potential primordial metabolism. The generative approach also has it intrinsic limitations: the unsupervised expansion of the chemical space remains infeasible due to the exponential growth of possible molecules and reactions between them. Here, in particular, the combinatorial complexity of the HCN polymerisation and hydrolysation networks forms the computational bottleneck. As a consequence, guidance of the computational exploration by chemical experience is indispensable.
WIDENING THE CIRCLE OF SECURITY: A QUASI‐EXPERIMENTAL EVALUATION OF ATTACHMENT‐BASED PROFESSIONAL DEVELOPMENT FOR FAMILY CHILD CARE PROVIDERS
Authors: Gray Sarah A. O.
Published: May 2015

This pilot program evaluation was undertaken to examine the effectiveness of an attachment‐based, group professional‐development experience, Circle of Security‐Parenting, on family childcare (FCC) providers' psychological resources and self‐efficacy in managing children's challenging behaviors and supporting children's socioemotional development. Licensed FCC providers with children actively in their care (n = 34) self‐selected into the program, offered in English and Spanish through a regional support network for FCC providers; a comparison group of providers was recruited from the state database of licensed providers (n = 17). A significant Time × Group interaction was observed for self‐efficacy in managing challenging behaviors, F(1, 46) = 30.59, p = .000, partial η2 = .40, with participating providers' mean self‐efficacy scores increasing, p = .000, d = .78, while comparison providers’ decreased, p = .003, d = 1.40. Mean depressive symptoms decreased over time for both groups whereas job stress‐related resources were stable over time in both groups. Patterns of association were found between providers’ self‐report of difficulties considering children's mental states and depressive symptoms, job stress resources, and self‐efficacy. Limitations and implications for future research are reviewed, including the impact of conducting this work within an organized support network for FCC providers.
In vivo bone formation by human alveolar‐bone‐derived mesenchymal stem cells obtained during implant osteotomy using biphasic calcium phosphate ceramics or Bio‐Oss as carriers
Authors: Park Jung‐Chul , Oh Sang‐Yeob , Lee Jung‐Seok , Park So‐Yon , Choi Eun‐Young , Cho Kyoo‐Sung , Kim Chang‐Sung
Published: May 2015

Objectives

The aim of this study was to evaluate HA coated with different ratios of TCP as a carrier for hABMSCs obtained during implant osteotomy in comparison to slowly‐resorbing biomaterial, Bio‐Oss, as a negative control, using in vitro and in vivo experiments.

Materials and Methods

Human ABMSCs (hABMSCs) harvested during implant osteotomy were transplanted using HA/TCP or Bio‐Oss as carriers in a murine ectopic transplantation model (n = 12). Pore size and cell affinity were evaluated in vitro. The area of newly formed bone was analyzed histometrically, the number of osteocytes was counted, and immunohistochemical staining was conducted against several markers of osteogenesis, including alkaline phosphatase (ALP), runt‐related transcription factor 2 (RUNX‐2), osteocalcin (OCN), and osteopontin (OPN). Osteoclast formation was evaluated by tartrate‐resistant acid phosphatase staining.

Results

The carrier materials had comparable pore sizes. The cell affinity assay resulted in a high proportion of cell adhesion (>90%) in all experimental groups. Substantial new bone and osteocyte formation was observed on both HA/TCP carriers, whereas it was minimal with Bio‐Oss. Positive immunostaining for ALP, RUNX‐2, OCN, and OPN was observed with HA/TCP, but only limited expression of osteogenic markers with Bio‐Oss. Conversely, there was a minimal osteoclast presence with Bio‐Oss, but a significant presence of osteoclasts with both HA/TCP carriers.

Conclusions

Both types of scaffolds, BCP and Bio‐Oss, showed high stem cell‐carrying potential, but the in vivo healing patterns of their complexes with hABMSC could be affected by the microenvironment on the surfaces of the scaffolds. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 515–524, 2016.
Determination of Total Selenium in Human Urine and Serum by Graphite‐Furnace Atomic‐Absorption Spectrophotometry with Palladium‐Nickel‐Ammonium Nitrates as a Matrix Modifier
Authors: Kao Chih‐Ming , Cherng Yunn‐Jing , Wung Ming‐Hong , Tsao Pi‐Yuan , Kuo Mao‐Sung
Published: May 2015

After human urine or serum was diluted (1 + 9) with HNO3 (0.2%, v/v) and standard additions of Se solution (100 μ L−1), the diluted sample (10 μL) was introduced into the graphite cuvette. The matrix modifier [10μL, containing Pd (0.6 μg) + Ni (25 μg) + NH4NO3 (80 μg) in HNO3 (0.2%, v/v) for urine, or Pd (0.3 μg) + Ni (30 μg) + NH4NO3 (80 μg) + Triton X‐100 (0.04%) in HNO3 (0.2%, v/v) for serum, respectively] was added and the mixture was heated according to a temperature program. The matrix modifier containing NH4NO3 in a suitable amount and a small amount of Pd enhanced the sensitivity for Se. The method detection limits (3σ) after dilution were about 4.9 ± 0.8 and 2.36 ± 0.18 μg L−1 for urine and serum, respectively. The accuracy of this method was tested with SRM #2670 human urine Se and Seronorm Trace Elements #116 human serum Se, respectively, and the results of 97.6 – 101% and 100 – 104% were obtained with precision ± 0.3% and ± 2%, respectively. This method can be applied easily and accurately to the determination of concentration of total Se in human urine and serum.
Tricarbonyl(N,N‐Disubstituted‐Cyclohexadienecarboxamide)iron Complexes: Investigation of the Possible Intramolecular Interaction between the Iron Center and the Amide Substituent
Authors: Pcrng Ming‐Tzong , Yu Wei‐Ren , Hwang Wen‐Shu
Published: May 2015

Direct reaction of iron pentacarbonyl with 1‐N,N‐disubstituted‐cyclohexa‐2,5‐dicnecarboxamide and 1‐N,N‐disubstituted‐cyclohexa‐1,3‐dienecarboxamide mixture (in which the disubstkuted group is diethyl or diphenyl) gave the isomeric tricarbonyl iron complexes of 2‐N,N‐disubstituted‐1,4‐η‐cyclohexa‐1,3‐dienccarboxamide (1), 1‐N,N‐disubslituted‐1,4‐η‐cyclohexa‐1,3‐dienecarboxamide (2), and 5‐N,N‐disubstituted‐1,4‐η‐cyclohexa‐1,3‐dienecarboxamide (3) and tricarbonyliron complexes of l‐N,N‐disubstituted‐cyclohexenecarboxamide (4). These complexes were separated and characterized by IR, UV‐VIS, 1H NMR, elemental analysis, and mass spectra. Only 1 isomerized to give 2 under acidic conditions; both 1 and 2 undergo hydride abstraction with triphenylmethyl hexafluorophosphatc. Complexes 3, undergo neither isomcrization nor hydride abstraction. According to the spectral data, the possible interaction between carboxamide and iron carbonyl moiety was investigated. The irreversible electrochemical behavior of these complexes were studied.
Synthetic Applications of Carbonyl Ylides Generated via the Tandem Cyclization Cycloaddition Reaction of Rhodium Carbenoids
Authors: Padwa Albert
Published: May 2015

The author's chemical studies dealing with the generation of carbonyl ylides via the rhodium(II) induced cyclization of α‐diazo alkanediones are summarized, Dipole formation occurs by reaction of a transient rhodium carbenoid intermediate with a neighboring carbonyl group. These cyclizations are performed under extremely mild conditions, typically at room temperature in a neutral organic solvent. Since these cycloadditions involve carbonyl ylides, the resulting products are oxabicycles of varying ring size. When the dipolarophile is intramolecularly tethered to the dipole, the subsequent cycloaddition affords complex oxapolycyclic systems with three (or more) component rings.
Synthesis and Photoproperties of Silicon Phthalocyanines and Silicon Naphthalocyanines
Authors: Wen Tsai‐Chuan , Liu Min‐Eng , Young Su‐Hay , Lee Ya‐Su , Chen Kuo‐Mei , Kuo Chen‐Nan
Published: May 2015

Silicon phthalocyanines and silicon naphthalocyanines, which are two derivatives in the family of hematoporphyrin, have been synthesized to assess their potential as photosensitizers for photodynamic therapy. For these complexes the red shift of their Q‐band maximum absorption tends to depend on the nature of the axial substituent. The bimolecular rate coefficients for the interacting between photosensitizer, either SiNC or SiPC, and generated singlet molecular oxygen were determined from the time‐resolved emission spectrum of singlet oxygen at 1.27 μm. On the basis of these data the electron‐transfer quenching mechanism is discussed in relation to the Marcus model.
Solvent‐Mediated Iodine Intercalation of a High‐Tc Oxide Superconductor Bi2Sn1.8Ca1.2CU2Ox
Authors: Guo T. N. , Chen Teng‐Ming
Published: May 2015

The benzene‐mediated iodine intercalation into the pseudo‐layered superconductor Bi2Sr1.8Ca1.2Cu2Ox (2212) is an efficient way to prepare an intercalate with nominal composition IBi2Sr1.8Ca1.2Cu2Ox. Expansion by 22 percent along the crystallographic c‐axis was observed but both a‐and b‐axes of the intercalates remained unchanged. The superconducting temperature (Tc) of 2212 phase decreased 10 K upon iodine intercalation. We report the First solvent‐mediated intercalation reaction and preliminary characterizations of a presumably stage‐1 phase IBi2Sr1.8Ca1.2Cu2Ox.
Enantioselective Synthesis of β‐Lactam Carried C(3) Functionality via Ester Enolate‐Imine Condensation
Authors: Lee Chih‐Shone , Chen Hsiu‐Ho
Published: May 2015

Enantioselective synthesis of optically active β‐lactam via ester enolate‐imine condensation using homochiral ester 16 and imine 17 provided β‐lactam 18a in 77% cc. Lactam 18a, carried C(3) functionality on β‐lactam nuclei, provided a potential precursor toward a synthesis of dipeptide antibiotic.
Heterocyclic Synthesis with Enamines: Convenient Syntheses of Polyfunctionally Substituted Pyrazole, Pyridine, Pyrimidine and Pyrazolo[3,4‐d]pyrimrdine Derivatives
Authors: Mohareb Rafat Milad , Sherif Sherif Mourad , Zohdi Hussein Fouad
Published: May 2015

Facile syntheses of pyrazole, pyridine, pyrimidine and pyrazolo[3,4‐d]pyrimidine derivatives have been achieved by the reaction of β‐enamino nitrile 2a with hydrazines, phenyl isothiocyanate, thiourea and active methylene reagents. The β‐enamino ketone 2e with the same reagents affords 3,5‐dimethyl heterocyclic ring systems.
Preconcentration of Metal Ions with Anion‐Exchange Resin
Authors: Jen Jen‐Fon , Fu Jen‐Tong
Published: May 2015

A method to preconcentrate metal ions employed an anion‐exchange resin was studied. Metal ions were first chelated with ethylenediaminetetraacetic acid (EDTA), then trapped on an enrichment column packed with anion‐exchange resin. The major interfering ions, e.g. calcium and magnesium were excluded from enrichment by appropriate adjustment of pH. Desorption of the trapped metals was effected by elution with HCl (0.1 M). Recoveries of Cu2+, Ni2+, Co2+, Pb2+, Zn2+ reached 99%. By comparison with preconcentration methods using cation‐exchange resin, this method has the advantages of selectivity, quantitative recovery, small cost of operation, and simple procedure.
The 4α‐Methylsterol Violasterol A from Viola Formosana Hayata
Authors: Lee Shwu‐Woan , Chen Zong‐Tsi , Chen Chiu‐Ming
Published: May 2015

A new 4α‐methylsterol, violasterol A, with three known flavonoids‐luteolin, luteolin 7‐O‐β‐D‐glucoside and tricin‐were isolated from ethanolic extract of whole plants of Viola formosana. The structure of vioiasterol A was assigned to be (22E)‐4α‐methyl‐24ξ‐isopropenyl‐5α‐cholesta‐7, 22‐diene‐3β‐ol (1) on the basis of spectral and chemical evidence.
Alkylation of Ethylbenzene with Methanol on HY, HM and HZSM‐5 Zeolite
Authors: Ko An‐Nan , Huang Chin Shyuaan
Published: May 2015

The alkylation of ethylbenzene with methanol on various zeolites has been studied at atmospheric pressure, 300–500 °C and with ethylbenzene/methanol = 3 mol/mol in a fixed‐bed, integral‐flow reactor. The catalytic activity decreased in the order HZSM‐5 > HY > HM. The optimum conditions for the formation of ethyltoluene were HY zeolite, 400 °C and W/F = 4.1 g‐cat h/g‐feed. The catalyst decay rate increased in the order HZSM‐5 << HY < HM; coking of the zeolite increased the fraction of para‐isomer in the ethyltoluenes. On HZSM‐5 modified with alkaline earth metal, the conversion of ethylbenzene decreased with concomitantly increased selectivity of para‐ethyltoluene especially evident in cases of magnesium and calcium (> 93% para‐selectivity). These results are interpreted in terms of diminution of both the strong acid sites and the pore size of zeolites. For the reaction on HY at 400 °C, the reaction paths were determined; the ethylbenzene reacted via alkylation, disproportionation and dealkylation with initial selectivities 84.7%, 13.1% and 2.2%, respectively.
Constituents of Houttuyniae Cordata and the Crystal Structure of Vomifoliol
Authors: Jong Ting‐Ting , Jean Meei‐Yueh
Published: May 2015

In the isolation of the constituents of Houttuyniae cordata, ten pure compounds including 1,3,5‐tridecanoylbenzene (1), caryophyllene oxide (2), several sterones (3‐6) and sesamin (7), plus long‐chain alcohol mixture, a steroidal mixture and 4‐hydroxybenzoic acid methyl ester (8), vomifoliol (9) [or Blumenol A], quercetin‐3‐O‐β‐L‐rhamnoside (10), were isolated from the aerial parts of H cordata. Their structures were determined by spectral analysis. Among them, compound 1 is for the first time isolated from nature. We describe here the spectral analysis of 1, and the X‐ray determination of the relative stereochemistry of vomifoliol (9).
A Novel Canthin‐6‐One Alkaloid Isolated from Cell Suspension Cultures of Brucea Javanica (L.) Merr
Authors: Chen Karin Chiung‐Sheue , Chang Hui‐Li , Chan Mei‐Ling , Lee Shoei‐Sheng
Published: May 2015

During investigation of cell suspension cultures of Brucea javanica (L.) Merr., the canthin‐6‐one alkaloid 5,11‐dimethoxycanthin‐6‐one (1) was isolated. The structural determination is based on spectral analysis. Five other alkaloids, canthin‐6‐one‐3‐N‐oxide (2), 11‐hydroxycanthin‐6‐one (3), canthin‐6‐one (4), 5‐methoxycanthin‐6‐one (5), and 11‐methoxycanthin‐6‐one (6), were also identified.
Xenon Adsorption and Xe‐129 NMR on Faujasite Zeolites
Authors: Shy Dcr‐Shiuh , Chao Kuei‐Jung
Published: May 2015

Faujasites of Si/Al = 2–5 were obtained by direct synthesis and (NH4)SiF6 dealumination. The dependence of their Xe‐129 NMR and xenon adsorption isotherm on Al content was used to monitor the inhomogeneous distribution of Al in synthesized samples of faujasite.
Measurement of the Hydrolysis of Tin Tetraacetate by Proton and Carbon‐13 NMR Spectroscopy
Authors: Lin Hann‐Jenn , Lin Yun‐Huin , Chen Jyh‐Horung , Hwang Lian‐Pin
Published: May 2015

Solid‐state l3C CP/MAS spectral analysis of the hydrolysis products of Sn(OAc)4 allowed the hydrolysis intermediates, Sn(OH)(OAc)3, Sn(OH)2(OAc)2 and Sn(OH)3(OAc), to be identified. The results show that the hydrolysis consists of three steps; the first and second steps are consecutive reactions and the third is reversible. Intermolecular exchange between hydrolysis products (i.e. Sn(OAc)4, Sn(OH)(OAc)2, Sn(OH)2(OAc)2 and Sn(OH)3(OAc),) and acetic acid was observed from the measurement of 1H and 13C solution spectra at varied temperatures in CD2Cl2 with ΔG‡348 50.5 kJ mol−1.
Synthesis of 6,13‐Dihydroxyimino‐5,12‐Dimethyl‐ 7,14‐Dioxo‐1,4,8,11‐Tetraazacyclotetradeca‐4,11‐Diene
Authors: Lin Cheng‐Hsien
Published: May 2015

6,13‐Dihydroxyimino‐5,12‐dimethyl‐7,14‐dioxo‐1,4,8,11‐tetraazacyclotetradeca‐4,11‐diene 2 was prepared by condensation of ethyl α‐oximinoacetoacetate with ethylenediamine in tetrahydrofuran at room temperature. Reduction of 2 gave the corresponding 6,13‐dihydroxyimino‐5,12‐dimethyl‐7,14‐dioxo‐1,4,8,11‐tetraazacyclotetradecane 3. Acylation of 2 afforded 6,13‐bis(O‐acetoxyimino)‐5,12‐dimethyl‐7,14‐dioxo‐1,4,8,1 l‐tetraazacyclotetradeca‐4,11‐diene 4. The structures of 2, 3 and 4 were determined by IR, NMR and mass spectroscopy.
Substituent Effects on the Chemical Reactivities of Tricarbonyl and Tetracarbonyl Iron Complexes of 7‐Azanorbornadiene Derivatives
Authors: Huang Hai‐Wei , Lee Shyi‐Long , Chow Tahsin J.
Published: May 2015

The intermediates of nitrene‐extrusion reaction were found in the forms of (ANB)Fe(CO)4 or (ANB)Fe(CO)3 during the reaction of 7‐azanorbornadiene derivatives (ANB) with diiron nonacarbonyl. By using extended Hückel molecular orbital (EHMO) calculation, we found that the chemical behavior of these complexes is correlated with the nature of substituents of ANB. The relative reactivity of (ANB)Fe(CO)4 and (ANB)Fe(CO)3 is influenced by the charge distributions on iron and nitrogen. In the crystal structure of (ANB)Fe(CO)4 an angular distortion of Fc‐C=O is observed, which is a result of donor‐acceptor interaction between the lone‐pair of N and the π* orbital of CO.
Catalytic Properties of Layered and Pillared Buserite
Authors: Wong She‐Tin , Cheng Soofin
Published: May 2015

The catalytic properties of Na‐buserite and Keggin ion‐pillared buserite (abbreviated as KPB) in the oxidation of ethane, were investigated with varied mixtures of ethane and air. Na‐buserite Na4Mn14O26 xH2O is a layered manganese oxide, KPB was prepared by the introduction of aluminium Keggin ions, [Al13O4(OH)24(H2O)12]7+ into the interlayers. Pillaring of the interlayers increases the active surface area participating in the reactions, as indicated by greater conversion over KPB than over a Na‐buserite catalyst. In an oxygen‐rich environment, complete combustion of ethane is achieved at temperatures ≈︁ 350 °C over KPB, and the structure of KPB is retained. The structure of KPB is less stable than that of Na‐buserite in an oxygen‐poor environment, and it disintegrates at large conversion. This phenomenon is explained in terms of the oxygen deficiency in the interlayer at a large reaction rate. Similar effects were absent from an oxygen‐rich environment. The variation of the product selectivity of Na‐buserite and KPB catalysts is discussed in terms of the presence of interlayer reaction sites.
Molecular Structure of a Binuclear Copper(II) Complex: [Cu2L2DMF2]·DMF·2ClO4 (LH = 4‐Methyl‐2,6‐Bis(indazol‐2‐Ylmethyl)phenol)
Authors: Chang Wen‐Kuen , Lee Gene‐Hsiang , Wang Yu , Oliver Su Y. , Ho Tong‐Ing , Lin Yuan‐Chuan
Published: May 2015

The molecular structure of a binuclear copper(II) complex [Cu2L2DMF2]·DMF·2ClO4 in which LH is 4‐methyl‐2,6‐bis (indazol‐2‐ylmethyl)phenol and DMF is N,N‐dimethylformamide is reported. The structure of the crystal was characterized by X‐ray diffraction: monoclinic, space group P21/C, Z = 2, a = 15.863(4), b = 20.642(3),c = 19.598(5) Å, β = 113.05(2)°. The final R and Rw values are 0.060 and 0.061, respectively, for 4777 reflections with I > 2σ(I). Each copper(II) is penta coordinate, with two N atoms from the indazole ring, two O atoms from phenolate in ligands and another O atom from DMF to form a distorted square‐pyramid. The mean value of the lengths of the four Cu‐N bonds is 1.987(6) Å and the Cu ⃛Cu distance is 3.094(1) Å No EPR signal was detected, and the magnetic moment has a small value μ = 1.17 per copper. These results indicate strong antiferromagnetic interaction between the two copper(II) ions.
Photoaddition of Tertiary Amines to 2‐Cyclopentylidenecyclopentanone
Authors: Huang Tian‐Chyuan , Ho Tong‐Ing
Published: May 2015

Photochemical reactions of 2‐cyclopentylidenecyclopentanone with diisopropylmethylamine, diisopropylethylamine, dimethylaniline, triethylamine, isopropyldimethylamine and dimethylbutylamine in acetonitrile were studied. Besides the addition product, a novel 3+2 cycloaddition adduct 3a‐hydroxytrispiro(octahydropentalene‐1,1′:2,1″:3,1‴‐triscyclopentane)‐2‴‐one was isolated. The quantum yield and Stern‐Volmer parameters with triplet quencher piperylene are reported. From these kinetic studies of mechanism photo‐induced electron transfer and proton transfer is proposed for formation of the novel 3+2 cycloadduct of 2‐cyclopentylidenecyclopentanone.