bluuebunny/crossref_metadata_2025 huggingface dataset:
Impact of Total Knee Arthroplasty as Assessed Using Patient‐Reported Pain and Health‐Related Quality of Life Indices: Rheumatoid Arthritis Versus Osteoarthritis
Authors: Dusad Anand , Pedro Sofia , Mikuls Ted R. , Hartman Curtis W. , Garvin Kevin L. , O'Dell James R. , Michaud Kaleb
Published: July 2015

Objective

To assess and compare the impact of total knee arthroplasty (TKA) in patients with rheumatoid arthritis (RA) and patients with osteoarthritis (OA).

Methods

Patients with rheumatologist‐diagnosed arthritis undergoing primary TKA during 1999–2012 were identified. Indices of pain (overall, index knee, and contralateral knee) and health‐related quality of life (HRQOL) were obtained in 3 consecutive 6‐month intervals: preoperative (baseline), perioperative, and postoperative (recovery). Descriptive statistics and one‐way analysis of variance were used to compare TKA outcomes by diagnosis. Effect sizes and standardized response means (SRMs) were calculated between baseline and recovery.

Results

Of the participating 18,897 patients, 834 of those with RA (5.3%) and 315 of those with OA (10.2%) had undergone index TKA at similar mean ages (65 and 68 years). Post‐TKA, significant improvements were observed for most domains of pain, function, and HRQOL within both disease groups, with greater impact in OA. Based on the SRM, the maximum improvement was shown in index knee pain (SRM −1.33 in RA and −1.34 in OA; effect size −1.75 and −1.94, respectively). The Health Assessment Questionnaire II and the Short Form 36 physical component summary were the most responsive HRQOL indices in detecting post‐TKA improvement in RA. A diagnosis of RA, lower income, and preoperative anxiety were independently associated with a lower degree of improvement in index knee pain following TKA.

Conclusion

TKA is highly effective in reducing clinically relevant knee pain (to a greater extent than its effect on other subjective HRQOL indices in patients with RA), although this improvement is less marked as compared to that among patients with OA. TKA serves as a “time machine” via which patients can return to a lifestyle with less disability, before the arthritis process catches up in RA.
Synthesis of Novel Triazolo Cyclobutane Nucleoside Analogs
Authors: Tran Thi Thu Thuy , Ngo Ngoc Thang , Dinh Thi Ha , Vo‐Thanh Giang , Legoupy Stéphanie
Published: July 2015

Synthesis of triazolo‐cyclobutane nucleosides analogs is reported. These molecules have been obtained by a short and efficient sequence involving a click azide‐alkyne cycloaddition following by cis‐hydroxylation in the key step.
Synthesis and Biological Evaluation of N3‐Alkyl‐Thienopyrimidin‐4‐Ones as mGluR1 Antagonists
Authors: Kim Minjoo , Kim Youngjae , Seo Seon Hee , Baek Du‐Jong , Min Sun‐Joon , Keum Gyochang , Choo Hyunah
Published: July 2015

Metabotropic glutamate receptor subtype 1 (mGluR1) is a potential target for the treatment of neuropathic pain, and there has been much effort to discover mGluR1 antagonists. In this study, a series of N
3‐alkyl‐thienopyrimidin‐4‐ones were prepared by introducing various alkyl and aryl groups to the N
3‐ and 7‐positions of the thienopyrimidin‐4‐one core structure, respectively, and their inhibitory activities against mGluR1 were biologically evaluated. Structure–activity relationship study revealed that the trans‐4‐methylcyclohexyl, cycloheptyl, and cyclooctyl groups at N
3‐position, and 2‐fluorophenyl group at 7‐position were most effective in potentiating the inhibitory activity of the thienopyrimidin‐4‐one derivatives against mGluR1. Among the synthesized compounds, 3‐cyclooctyl‐7‐phenylthienopyrimidin‐4‐one and 3‐cycloheptyl‐7‐(2‐fluorophenyl)thienopyrimidin‐4‐one exhibited the most potent inhibitory activities with IC50 values of 115 and 107 nM, respectively.
Synthesis and Characterization of Carbon Nanofibers Grown on Ni and Mo Catalysts by Chemical Vapor Deposition
Authors: Jang Eunyi , Park Heai‐Ku , Choi Jong‐Ha , Lee Chang‐Seop
Published: July 2015

In this study, we synthesized carbon nanofibers using Ni and Mo catalysts by chemical vapor deposition. Catalysts used in the synthesis of carbon nanofibers were prepared by changing the molar ratio of nickel nitrate and ammonium molybdate. Precipitates were then obtained by reacting with ammonium carbonate. The optimum temperature for synthesis of carbon nanofibers was found by changing it between 600 and 800 °C. At these temperatures, carbon nanofibers were synthesized with various ratios of catalysts. Structural and physiochemical properties were analyzed by scanning electron microscopy, energy dispersive spectroscopy, X‐ray diffraction, Raman, and X‐ray photoelectron spectroscopy. The specific surface area of synthesized carbon nanofibers was measured by BET. It was found that characterization of carbon nanofibers were significantly affected by the synthesis temperature and the concentration ratio of metal catalysts. When the catalyst with the concentration ratio of Ni and Mo was 6:4 at 800 °C, uniform carbon nanofibers with a diameter of 50 nm were grown. Crystallinity and amorphicity of the synthesized carbon nanofiber were excellent compared to those of carbon nanofibers synthesized with metal catalysts in different concentration ratios. A three‐electrode cell was prepared by using the synthesized carbon nanofibers as anode of Li secondary battery. The electrochemical properties of carbon nanofibers were examined through cyclic voltammetry and galvanostatic charge–discharge.
Synthesis of 6‐ or 8‐Bromo Flavonoids by Regioselective Mono‐Bromination and Deprotection Protocol from Flavonoid Alkyl Ethers
Authors: Pan Guojun , Yang Ke , Ma Yantao , Zhao Xia , Lu Kui , Yu Peng
Published: July 2015

C‐6 and C‐8 monobromo flavonoids are important building blocks for the synthesis of flavonoid natural products and their derivatives. Bromination of suitably alkylated flavonoids with N‐bromosuccinimide in dichloromethane (DCM), followed by deprotection with BCl3
, gives either a C‐6 or a C‐8 monobromo flavonoid in high yield and with high regioselectivity, depending on the protection pattern of the C‐5 and C‐7 OH groups. The mild and neutral conditions are particularly useful for the regioselective bromination of acid‐labile substrates.
mPW1PW91‐Calculated Structures, IR Spectra, and Frontier Orbitals of 1,2‐Bridged Calix[4]aryl Picrate Complexed with Alkali Metal Ions
Authors: Ham Seung Wook , Choe Jong‐In
Published: July 2015

The molecular structures of three conformers (cone [CONE], partial cone [PACO], and 1,2‐alternate [12A]) of 1,2‐bridged calix[4]aryl picrate 1 and their alkali‐metal‐ion complexes were optimized using a mPW1PW91/6‐31G(d,p) (hybrid HF–DF) calculation method. The total electronic and relative binding energies and the gaps of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) frontier orbitals of the complexes of each conformer with sodium and potassium ions were analyzed. The HOMOs are mainly concentrated in the phenyl rings in calix skeleton as bonding orbitals, while the LUMOs are located in the picrate moieties as anti‐bonding orbitals. The monotopic binding efficiency of the 1(CONE)·Na+(exo) complex (−98.0 kcal/mol) was the strongest among the six kinds of the Na+ complexes and much better than that of the 1(12A)·K+(exo) complex (−77.8 kcal/mol). The IR spectra of the conformers of 1 and their complexes with the alkali metal ions were calculated by mPW1PW91 and analyzed.
Photoelectrochemical Performances of Hematite (α‐Fe2O3) Films Doped with Various Metals
Authors: Bak Ayoung , Choi Sung Kyu , Park Hyunwoong
Published: July 2015

Hematite (α‐Fe2O3
) film electrodes doped with 14 different metal cations are fabricated using one‐step co‐electrodeposition techniques and their photoelectrochemical (PEC) performances are compared in a 1 M NaOH electrolyte under AM 1.5 irradiation. Identical doping levels of Pt(II and IV), Ce(III), Cd(II), Al(III), and Sn(IV) at 5 at.% improve the PEC performance of hematite, whereas Co(II), Ni(II), Cu(II), Ru(III), and Pd(II) reduce the performance. Doping with Ag(I), Cr(III), Ir(IV), and Au(III) have little effect on the performance. The doping effects of Pt(II), Cd(II), Ag(I), and Cr(III) are studied in greater detail using various surface analysis techniques (scanning electron microscopy, X‐ray photoelectron spectroscopy, X‐ray diffraction, and UV–Vis diffuse reflectance) and electrochemical analysis techniques (Mott–Schottky and impedance) by varying the doping levels (0–10%). Metal doping increases the primary particle sizes of hematite from ca. 50 nm to 70–100 nm due to interparticle agglomeration, and shifts the binding energies of the O 1s bands in the XPS spectra. The energetics of the bare and doped hematite (bandgap, conduction, and valence band levels) are estimated from the spectral responses and Mott–Schottky analyses. Pt, Cd, and Ag increase the bandgap by 0.06 eV but Cr reduces it by 0.06 eV. All doped hematite electrodes have valence band levels positive (~1.1 V) of water oxidation. At optimal doping levels, Pt(8%) improves the PEC performance of hematite approximately 3.2 times, whereas Cd(2%) and Ag(5%) increase it around twofold and 60%, respectively. The different optimal doping levels are discussed in terms of the depletion layer, electrical conductivity, and energy levels. The enhanced PEC performance of the doped hematite electrodes are attributed primarily to the increased electrical conductivity.
Kinetic Study on Quinuclidinolysis of O‐4‐Nitrophenyl X‐substituted Thionobenzoates and O‐3,4‐Dinitrophenyl Thionobenzoate: Effect of Amine Nature on Reactivity and Reaction Mechanism
Authors: Yang Eun‐Ji , Kim Min‐Young , Um Ik‐Hwan
Published: July 2015

Second‐order rate constants (k
quin) have been measured spectrophotometrically for the reactions of O‐3,4‐dinitrophenyl thionobenzoate (1a) with a series of quinuclidine derivatives and of O‐4‐nitrophenyl X‐substituted thionobenzoates (2a–2f) with quinuclidine in 80 mol% H2O/20 mol% DMSO at 25.0 ± 0.1 °C. Quinuclidine is less reactive toward the thione esters than less basic benzylamine. Steric hindrance exerted by the tertiary amine is responsible for the decreased reactivity. The Hammett plot for the reactions of 2a–2f with quinuclidine consists of two intersecting straight lines, while the Yukawa–Tsuno plot for the same reactions exhibits an excellent linear correlation with ρ

X
= 1.10 and r = 0.71. This indicates that the nonlinear Hammett plot is not due to a change in the rate‐determining step but is caused by ground‐state stabilization of substrates possessing an electron‐donating group in the thionobenzoyl moiety through resonance interactions. Brønsted‐type plot for the reactions of 1a with quinuclidines is linear with β
nuc = 0.89, which is typical for reactions reported to proceed through a stepwise mechanism. However, the reactions have been concluded to proceed through a forced concerted mechanism. Instability of a plausible intermediate T± forces the reactions to proceed through such a mechanism.
Identification of Isomers of Organometallic Compounds
Authors: Mbue Sona Peter , Cho Kwang‐Hwi
Published: July 2015

The yaChI is a newly suggested chemical naming system. However, yaChI is a derivative of the IUPAC InChI with a modified algorithm that includes additional layers of chemical structure information. Consequently, yaChI string contains more structure details while preserving the original structure file information and can distinctively identify very closely related compounds reducing the chances of ambiguity in chemical compound databases as opposed to the general SMILES, InChI, and InChIKey. This study examines the relative performances of yaChI, SMILES, InChI, and InChIKey in duplication check for isomers. For simplicity, a small data set of 28 organometallic compounds (structural isomers of Rh‐containing compounds) subdivided into three major groups (A, B, and C) based on the number and the type of ligands attached to the center atom was used to study the performances of each encoding scheme in describing chemical structures. SMILES, InChI, and InChIKey were generated using Openbabel and RDkit, whereas yaChI strings were generated with in‐house program. Strings generated from SMILES, InChI, and InChIKey though different, resulted to only three unique chemical identifiers, with each belonging to one group indicating the presence of only three unique compounds in the study data. However, yaChI results depicted that all structures in each group are indeed unique and differ among themselves as well as those from other groups, mapping each structure with a unique identifier given a total number of 28 unique structures in the study data. This high perception of yaChI probe justifies its accuracy and reliability in duplication check among closely related compounds especially structures exhibiting stereo properties.
Synthesis and Characterization of Lead Zirconate Titanate Nanofibers Obtained by Electrospinning
Authors: Choi Sujin , Park Juyun , Kang Jisoo , Koh Sung‐Wi , Kang Yong‐Cheol
Published: July 2015

In this study, lead zirconate titanate (PZT) nanofibers were synthesized by electrospinning method using polyvinylpyrrolidone (PVP) as a viscosity controller and were characterized the crystallinity and the chemical composition ofPZTnanofibers obtained by different postannealing methods. From the X‐ray photoelectron spectroscopy results, the formation ofPZTnanofibers was confirmed. The diameter ofPZTnanofibers was a few hundreds of nanometers. And the diameter ofPZT‐D (directly annealed to the target temperature) nanofibers decreased as the annealing temperature increased while the diameter ofPZT‐S (stepwisely annealed to the target temperature) nanofibers increased which were confirmed bySEM. According to the results of X‐ray diffraction, as the annealing temperature increased, the crystallinity ofPZTnanofibers changed from pyrochlore to perovskite structure and the perovskite phase ofPZTwas observed from thePZTnanofibers annealed at823 K.
Synthesis and Biocompatibility of Silicone Hydrogel Functionalized with Polysaccharide
Authors: Jeong Keun‐Seung , Kim Ho‐Joong , Lim Hwa‐Lim , Ryu Geun‐Chang , Seo Eun‐Sun , You Nam‐Ho , Jun Jin
Published: July 2015

A novel methacrylated polydimethylsiloxane (mPDMS) was synthesized for the preparation of silicone hydrogel (SiHy). The SiHy was functionalized with polysaccharides such as hyaluronic acid and alginic acid by construction of an interpenetrating polymer network (IPN) structure composed of cross‐linked SiHy backbones and polysaccharide networks. We investigated the protein adsorption resistance, toxicity, wettability, optical transparency, and surface property of the SiHy. The synthesized SiHy exhibited the transmittance of over 90% and the improved surface hydrophilicity. Importantly, the amount of protein adsorbed on the polysaccharide‐functionalized SiHy decreased significantly compared with unmodified SiHy. These results suggest that polysaccharide‐modified SiHy may offer potential for ophthalmic materials as well as antibiofouling coating materials.
Preparation of 7‐Methoxy Tacrine Dimer Analogs and Their In vitro/In silico Evaluation as Potential Cholinesterase Inhibitors
Authors: Lee Sang Kwang , Park Min Kyun , Jhang Ho Eun , Yi Jinju , Nahm Keepyong , Cho Dae Won , Ra Choon Sup , Musilek Kamil , Horova Anna , Korabecny Jan , Dolezal Rafael , Jun Daniel , Kuca Kamil
Published: July 2015

Novel types of symmetric bis‐7‐methoxytacrines connected by oligoethyleneoxy chains 3–5 and nonsymmetric monomeric 7‐methoxytacrines containing hydroxyl‐terminated oligoethyleneoxy chains 6–8 were prepared, and their in vitro/in silico effects on human recombinant AChE (hAChE) and human plasmatic butyrylcholinesterase (hBChE) were compared, with 7‐MEOTA (2) as the standard compound. The symmetric bis‐7‐MEOTA derivatives 3–5 showed hAChE inhibition similar to that of 2. On the other hand, their effects on hBChE revealed an increasing inhibition trend when the oligoethyleneoxy units between the two 7‐MEOTA moieties became longer. Accordingly, compounds 4 and 5 showed better selectivity towards hBChE. The most effective in the inhibition hAChE and hBChE was compound 8 with the longest oligoethyleneglycol chain, whereas compounds 6 and 7 resulted in similar IC50 values. A molecular modeling study using substrates 5 and 8 showed a possible binding conformation and protein–ligand interaction between the substrates and AChE/BChE.
Topical Semisolid Formulations of Hirsutenone and Accelerated Stability Assessment
Authors: Kim Sung Rae , Jeong Kyu Ho , Lee Sang Gon , Kang Jong Bu , Kim Chae Jin , Kim Min Young , Yoon Kyu Hyeong , Lee Do Ik , Joo Seong Soo , Lee Min Won , Lee Sangkil , Choi Young Wook
Published: July 2015

To develop a topical preparation of hirsutenone (HST), a natural immunomodulator, we formulated oleaginous ointments and creams and assessed their stability in terms of shelf‐life. Ointments were prepared by mixing the molten lipid phase of white petrolatum and white beeswax with glycerin and propylene glycol, in which HST was dissolved with ascorbyl palmitate (AP), butylated hydroxyl toluene (BHT), or ethylenediaminetetraacetic acid (EDTA) as an antioxidant. Reference oil‐in‐water creams were formulated by conventional emulsification. The ointment and cream formulations were subjected to accelerated stability testing at 40 °C. At appropriate time points, test samples were dissolved in organic solvent, diluted with methanol, and filtered prior to high‐performance liquid chromatography (HPLC). The degradation of HST in cream and ointment formulations followed first‐order kinetics. The rate constants (day−1) of HST in cream and ointments were 1.71 × 10−2 and 0.67 × 10−2, respectively, revealing a 2.5‐fold greater half‐life in ointments than in creams. Although AP and BHT had no effect on chemical stabilization of ointments, EDTA enhanced the stability of HST at 40 °C. The shelf‐lives of HST formulations were estimated by the Q10 method. Assuming a Q10 value of 2, the shelf‐lives (days) of cream, ointment, and ointment with EDTA at 25 °C were 14.99, 38.23, and 44.19, respectively. At 4 °C, the shelf‐life of HST in ointment with EDTA was extended to 220 days. Even though the stability of HST was somewhat increased by the ointment formulation and further improved by adding EDTA, alternative approaches are needed to increase stabilization.
A Thermodynamic Study on Phthalide‐Type dyes in Aqueous Alcohol Solutions
Authors: Kim Jae‐Uk , Yoo Jeong‐Yeol , Kim Jong‐Gyu
Published: July 2015

Phthalide‐type dyes in aqueous variable alcohol solution were studied by UV–vis absorption spectroscopy. In this study, 7‐[4‐(diethylamino)‐2‐ethoxyphenyl]‐7‐(1‐ethyl‐2‐methyl‐1H‐indol‐3‐yl)furo[3,4‐b]pyridin‐5(7H)‐one (“Blue‐63”) was used. Generally, a blue shift is observed from dyes in higher‐carbon‐number‐alcohol solvents. The results indicated the dye equilibrium constant in aqueous alcohol solutions. The equilibrium constant (K), Gibbs energy change (∆G), enthalpy change (∆H), and entropy change (∆S) of the dye, depending on temperature change, were also calculated using UV absorbance.
Metal‐Free Aerobic Oxidative Esterification of Aldehydes in the Presence of Cyanide
Authors: Kim Yoo‐Jin , Cheon Cheol‐Hong
Published: July 2015

A metal‐free aerobic oxidative esterification of aldehydes in the presence of cyanide is described. Various aromatic aldehydes and sterically congested alcohols were amenable to this protocol. In addition, this method could be extended to the preparation of thioesters with a thiol in place of an alcohol. Furthermore, the cyanide‐mediated aerobic oxidation of aldehydes was applied to the synthesis of lactones via intramolecular esterification in the absence of an alcohol.
Phase I/II trial of capecitabine, oxaliplatin, and irinotecan in combination with bevacizumab in first line treatment of metastatic colorectal cancer
Authors: Bazarbashi Shouki , Aljubran Ali , Alzahrani Ahmad , Mohieldin Ahmed , Soudy Hussein , Shoukri Mohammed
Published: July 2015

Phase III studies have demonstrated the efficacy of FOLFOXIRI regimens (5‐fluorouracil/leucovorin, oxaliplatin, irinotecan) with/without bevacizumab in metastatic colorectal cancer (mCRC). Capecitabine is an orally administered fluoropyrimidine that may be used instead of 5‐fluorouracil/leucovorin. We evaluated a triple‐chemotherapy regimen of capecitabine, oxaliplatin, and irinotecan, plus bevacizumab in 53 patients with mCRC. A Phase I study identified the maximum tolerated dose of irinotecan as 150 mg/m2. Median follow‐up in a subsequent Phase II study using this dose was 28 months (74% progressed). For all patients, a complete response was achieved in 4% and a partial response in 60%; median progression‐free survival (PFS) was 16 months and median overall survival (OS) was 28 months. Median PFS was longer for patients with an early treatment response (28 vs. 9 months for others; P = 0.024), or early tumor shrinkage (25 vs. 9 months for others; P = 0.006), or for patients suitable for surgical removal of metastases with curative intent (median not reached vs. 9 months for others; P = 0.001). Median OS was longer for patients with early tumor shrinkage (median not reached vs. 22 months for others; P = 0.006) or surgery (median not reached vs. 22 months for others, P = 0.002). K‐ras mutations status did not influence PFS (P = 0.88) or OS (P = 0.82). Considerable Grade 3/4 toxicity was encountered (36% for diarrhea, 21% for vomiting and 17% for fatigue). In conclusion, the 3‐weekly triple‐chemotherapy regimen of capecitabine, oxaliplatin, and irinotecan, plus bevacizumab, was active in the first‐line treatment of mCRC, although at the expense of a high level of toxicity.
A Review on Gas Separation Applications of Supported Ionic Liquid Membranes
Authors: Karkhanechi Hanyeh , Salmani Saeide , Asghari Morteza
Published: July 2015

The selection of the separation process is a critical issue in the chemical industries. Among different conventional methods for the separation processes, supported liquid membrane (SLM)‐based separation processes have been predicted as a promising option. However, the industrial use of supported liquid membranes based on conventional liquids is limited by their relative instability and short lifetime. The use of ionic liquids as a liquid membrane phase results in the stabilization of the SLMs due to their negligible vapor pressure, possibility of minimizing their solubility in the surrounding phases and greater capillary force associated with their high viscosity, which can reduce the displacement of liquids from micron pores under pressure. In this review, recent advances in supported membranes based on ionic liquids including issues such as methods of synthesis IL, methods of preparation of supported ionic liquid membranes and application of supported ionic liquid membranes in gas separation are presented.
A One‐Step Staining Probe for Phosphatidylethanolamine
Authors: Hou Songwang , Johnson Steven E. , Zhao Ming
Published: July 2015

Phosphatidylethanolamine (PE) is an abundant phospholipid in cellular membranes, but relatively little is known about the kinetics of PE in biological membrane systems. Characterizing PE on a cellular level has been challenging owing to a lack of proper molecular tools. The lantibiotic duramycin and its structural analogue, cinnamycin, are currently the only known polypeptides that have an established stereospecific structure for binding membrane PE with high affinity and high specificity. These lantibiotics are recognized for their potential as molecular probes for studying PE kinetics in various membranes. However, owing to their antibiotic nature, duramycin and cinnamycin exhibit appreciable levels of cytotoxicity at low micromolar concentrations in cultured mammalian cells by inducing membrane distortion and possible PE redistribution. These issues can potentially complicate study design and data interpretation. Here, we report the construction of a molecular probe consisting of duramycin attached to the C terminus of green fluorescent protein (GFP) by a PEG linker at a stoichiometry of 1. The construct retained specific binding toward PE and essentially no cytotoxicity compared to native duramycin. The biological utilities of this probe were demonstrated in a number of cellular staining studies involving PE dynamics. The availability of a one‐step, nontoxic molecular probe for PE will enable characterization of the biology of this important phospholipid.
Efficient Photochemical Synthesis of Peptide‐α‐Phenylthioesters
Authors: Pardo Andrew , Hogenauer Tyrone J. , Cai Zhefeng , Vellucci Julian A. , Castillo Efrain M. , Dirk Carl W. , Franz Andreas H. , Michael Katja
Published: July 2015

Low yields and substantial epimerization of peptide‐α‐thioesters often compromise the overall efficiency of native chemical ligation (NCL). Peptide arylthioesters are more reactive than peptide alkylthioesters in NCL, but are also more difficult to handle due to their propensity to hydrolyze, and are therefore often generated in situ. However, pre‐prepared peptide arylthioesters are required for some NCL applications. Here we present a 7‐nitroindoline‐based photochemical method that generates protected peptide phenylthioesters under neutral reaction conditions via their activated esters from photoreactive peptide precursors in high isolated yields, and with low levels of epimerization. This method is fully compatible with Fmoc‐strategy solid‐phase peptide synthesis. Global deprotection with trifluoroacetic acid furnishes peptide phenylthioesters for NCL. Photoreactive peptide precursors can also be converted into their hydrazides in two steps by this method.
Cardiac rhythm abnormalities during intravenous immunoglobulin G(IVIG) infusion in two newborn infants: coincidence or association?
Authors: Tufekci Sinan , Coban Asuman , Bor Meltem , Yasa Beril , Nisli Kemal , Ince Zeynep
Published: July 2015

Key Clinical Message

We report the occurrence of supraventricular tachycardia during intravenous immunoglobulin (IVIG) infusion. Supraventricular tachycardia was observed in two newborn patients during IVIG infusion. Both of the babies responded to adenosine treatment. Cardiorespiratory monitoring during IVIG infusion can be recommended because of the possibility of this potentially lifethreatening adverse effect.
Synthesis and Peroxidase‐Like Activity of Cobalt@Carbon‐Dots Hybrid Material
Authors: Guo Yali , Liu Xiaoyu , Yang Chengduan , Wang Xudong , Wang Dan , Iqbal Anam , Liu Weisheng , Qin Wenwu
Published: July 2015

A cobalt@carbon‐dots (Co@C‐dots) hybrid material is successfully prepared and well characterized. The hybrid material exhibits intrinsic peroxidase‐like activity and can be utilized for the degradation of methylene blue; it shows enhanced catalytic activities compared with bare Co nanoparticles or C‐dots. The good catalytic performance of the hybrid material may be attributed to synergistic effects between the Co nanoparticles and C‐dots. Furthermore, the catalytic mechanism of the Co@C‐dots hybrid material is also studied by using steady‐state and time‐resolved fluorometric analysis, which reveals that Co@C‐dots can effectively decompose H2O2 to produce reactive hydroxyl radicals (.OH). These results suggest that the Co@C‐dots hybrid material could be a promising material applied for biochemical analysis and water treatment.
Mesoporous Biphasic C and N Codoped Anatase Nanocrystal–Carbon Composites and their Derived Doped Anatase Nanoparticles in Phenol Elimination under Visible Light
Authors: Zhu Xiaojuan , Wei Wei , Wan Ying
Published: July 2015

Mesoporous C and N codoped anatase nanocrystal–carbon composites have been synthesized by chelation‐assisted coassembly of urea, TiCl4, resols, and triblock copolymer. The composite catalysts have biphasic constituents in the pore walls of amorphous carbon and C,N‐codoped anatase nanoparticles (≈4.0 nm) that are “glued” together; the composite catalysts also have open mesopores with high surface areas (≈340 m2 g−1), large pore volumes (≈0.20 cm3 g−1), and uniform pore sizes (≈5.0 nm). Upon calcination in air at 350 °C, the main‐group‐elements‐codoped anatase nanoparticles with a size of 4.3 nm can be obtained. The C,N‐codoped anatase nanoparticles feature a clear redshift absorption towards the visible‐light region and exhibit remarkable degradation efficiency for phenol. A repeated accumulation–photodegradation process is adopted to remove high concentrations of phenol (100 mg L−1) from water, thereby avoiding the use of organic solvent and the posttreatment of the catalyst. After six cycles, phenol is almost completely degraded. The features of the two constituents of the composite are discussed. The mesoporous carbon support shows a high adsorption capacity for phenol, which accumulates inside its pores, and the main‐group‐elements‐doped anatase nanoparticles can be well accessible to phenol, which it mineralizes under artificial visible light. Simultaneously, the “glue” role of the amorphous carbon can overcome the disadvantages of possible particle aggregation during processes and allow the catalyst to be reused.
Effect of NiAl2O4 Formation on Ni/Al2O3 Stability during Dry Reforming of Methane
Authors: Zhou Lu , Li Lidong , Wei Nini , Li Jun , Basset Jean‐Marie
Published: July 2015

A series of alumina‐supported Ni catalysts were prepared to examine their activity and carbon deposition during dry reforming of methane (DRM). With an increase in the final calcination temperature to T=900 °C to form exclusively NiAl2O4, a catalyst with strong metal–support interactions was obtained. During a long‐term DRM reaction (of about t=100 h) at T=700 °C and with CH4/CO2=1:1, reduced Ni (from NiAl2O4) showed a high resistance to sintering and coking. The DRM kinetics behaviors of the catalysts calcined at different temperatures were also investigated. Carbon growth models were proposed to rationalize the different carbon morphologies observed on the catalysts.
DFT Mechanistic Investigation of the Gold(I)‐Catalyzed Synthesis of Azepino[1,2‐a]indoles
Authors: Giacinto Pietro , Cera Gianpiero , Bottoni Andrea , Bandini Marco , Miscione Gian Pietro
Published: July 2015

We describe a computational DFT investigation on the mechanism of the one‐pot synthesis of azepino‐indoles catalyzed by [Au(IPr)Cl]/AgOTf (IPr=1,3‐bis(2,6‐diisopropylphenyl‐imidazol‐2‐ylidene) by the simultaneous construction of the pyrrolyl and seven‐membered rings. The mechanism of the final ring‐closing event is elucidated, which reveals the counterion‐assisted nucleophilic trapping of the carbonyl moiety by the alkenyl‐gold species formed in situ. The computational evidence supports the labeling control experiments and highlights the presence of a cyclopropyl‐gold‐carbenoid intermediate in the final intramolecular 1,3‐hydrogen‐shift/skeleton‐rearrangement sequence.
Operando Attenuated Total Reflectance FTIR Spectroscopy: Studies on the Different Selectivity Observed in Benzyl Alcohol Oxidation
Authors: Villa Alberto , Ferri Davide , Campisi Sebastiano , Chan‐Thaw Carine E. , Lu Ye , Kröcher Oliver , Prati Laura
Published: July 2015

Au, Pd, and AuPd supported on TiO2 were prepared by a sol immobilization route. Operando attenuated total reflectance (ATR) IR spectroscopy and catalytic batch reactor experiments were performed in parallel to elucidate the different catalytic performance of the catalysts in the liquid‐phase oxidation of benzyl alcohol. Pd/TiO2 exhibited a higher activity than AuPd/TiO2 and Au/TiO2, but the modification of Pd with Au demonstrated a significant stability enhancement. ATR‐IR spectroscopy evidenced that the presence of Au facilitates the desorption of byproducts, which thus reduces the extent of deactivation of the active sites caused by the irreversible adsorption of benzoate species. Although benzaldehyde was the main product in both catalysts, the nature of the byproducts differs. Pd/TiO2 favored the deoxygenation of benzyl alcohol to produce toluene as the main byproduct. Conversely, AuPd/TiO2 promoted the transformation of benzaldehyde to benzoic acid.
Grafting of Copper(I)–NHC Species on MCM‐41: Homogeneous versus Heterogeneous Catalysis
Authors: Garcés Karin , Fernández‐Alvarez Francisco J. , García‐Orduña Pilar , Lahoz Fernando J. , Pérez‐Torrente Jesús J. , Oro Luis A.
Published: July 2015

The copper(I) complexes [Cu(X){2,6‐diisopropylphenyl–NHC–(CH2)3Si(OiPr)3}] (X=Cl (2 a); I (2 b), NHC=N‐heterocyclic carbene) have been synthesized and characterized. Furthermore, the structure of 2 b has been confirmed by X‐ray diffraction studies. Complex 2 a has been successfully anchored in MCM‐41 to afford 2–MCM‐41. The activity of both the homogeneous, 2 a, and heterogeneous, 2–MCM‐41, catalysts in acetophenone hydrosilylation with HSiEt3 and [3+2] cycloaddition of benzyl azide and phenylacetylene has been investigated. The heterogeneous catalyst exhibits catalytic activity for the cycloaddition reaction though, unexpectedly, shows no catalytic activity for hydrosilylation.
Toluene Oxidation by Hydrogen Peroxide in Deep Eutectic Solvents
Authors: Guajardo Nadia , Carlesi Carlos , Aracena Álvaro
Published: July 2015

The catalytic effect of several deep eutectic solvents (DESs) on biphasic toluene oxidation by hydrogen peroxide to produce benzaldehyde was studied under various operational conditions. Experiments were performed with sodium tungstate, iron(III) chloride, phosphotungstic acid, and phosphomolybdic acid as catalysts dissolved in three DESs composed of choline chloride and a hydrogen‐bond donor molecule such as urea, glycerol, or ethylene glycol. Additionally, a fourth catalytic system composed of iron(III) chloride and choline chloride was tested. The best result was achieved with FeCl3 dissolved in the DES containing ethylene glycol, which gave 37.9 % conversion and 63.6 % selectivity. The results are better than those reported for other ionic liquids; this may be due to similar activation of hydrogen peroxide by polarization of the peroxide bond through hydrogen bonding and the low viscosity of the solvent.
Comparison of Overall Gas‐Phase Mass Transfer Coefficient for CO2 Absorption between Tertiary Amines in a Randomly Packed Column
Authors: Wen Le , Liu Helei , Rongwong Wichitpan , Liang Zhiwu , Fu Kaiyun , Idem Raphael , Tontiwachwuthikul Paitoon
Published: July 2015

The mass transfer performance of CO2 absorption into an innovative tertiary amine solvent, 1‐dimethylamino‐2‐propanol (1DMA2P), was investigated and compared with that of methyldiethanolamine (MDEA) in a packed column with random Dixon‐ring packing. All experiments were conducted under atmospheric pressure. The effects of inert gas flow rate, amine concentration, liquid flow rate, CO2 loading, and liquid temperature on mass transfer performance were analyzed and the results presented in terms of the volumetric overall mass transfer coefficient (KGav). The experimental findings clearly indicate that 1DMA2P provided better mass transfer performance than MDEA. For both 1DMA2P and MDEA solutions, the KGav increased with rising amine concentration and liquid flow rate, but decreased with higher CO2 loading. The inert gas flow rate only slightly affected the KGav. A satisfactory correlation of KGav was developed for the 1DMA2P‐CO2 system.
Catalyst‐Assisted Electroless Flattening of Ge Surfaces in Dissolved‐O2‐Containing Water
Authors: Kawase Tatsuya , Saito Yusuke , Mura Atsushi , Okamoto Takeshi , Kawai Kentaro , Sano Yasuhisa , Morita Mizuho , Yamauchi Kazuto , Arima Kenta
Published: July 2015

Control of the microroughness of Ge surfaces is required to realize field‐effect transistors with high performances. We propose a novel surface‐flattening process for Ge that involves the preferential transformation of surface protrusions on Ge into soluble GeO2 with the help of a catalyst in water. To carry out this process, we developed a setup comprising a catalyst plate covered with a Pt film in contact with a Ge surface in saturated O2‐dissolved water. The role of the metallic film is to enhance the oxygen reduction reaction in water that accompanies the oxidation of protrusions or microbumps on a Ge surface. After presenting the fundamental etching properties of a Ge surface treated with this metal‐assisted chemical etching method, we demonstrate that our water‐based process creates a flattened Ge surface that has few protrusions with a lateral size on the order of 10 nm.
Radical CH Alkylation of BODIPY Dyes Using Potassium Trifluoroborates or Boronic Acids
Authors: Verbelen Bram , Cunha Dias Rezende Lucas , Boodts Stijn , Jacobs Jeroen , Van Meervelt Luc , Hofkens Johan , Dehaen Wim
Published: July 2015

A one‐step synthetic procedure for the radical CH alkylation of BODIPY dyes has been developed. This new reaction generates alkyl radicals through the oxidation of boronic acids or potassium trifluoroborates and allows the synthesis of mono‐, di‐, tri‐, and tetraalkylated fluorophores in a good to excellent yield for a broad range of organoboron compounds. Using this protocol, multiple bulky alkyl groups can be introduced onto the BODIPY core thus creating solid‐state emissive BODIPY dyes.
Creating σ‐Holes through the Formation of Beryllium Bonds
Authors: Brea Oriana , Mó Otilia , Yáñez Manuel , Alkorta Ibon , Elguero José
Published: July 2015

Through the use of ab initio theoretical models based on MP2/aug‐cc‐pVDZ‐optimized geometries and CCSD(T)/aug‐cc‐pVTZ and CCSD(T)/aug‐c‐pVDZ total energies, it has been shown that the significant electron density rearrangements that follow the formation of a beryllium bond may lead to the appearance of a σ‐hole in systems that previously do not exhibit this feature, such as CH3OF, NO2F, NO3F, and other fluorine‐containing systems. The creation of the σ‐hole is another manifestation of the bond activation–reinforcement (BAR) rule. The appearance of a σ‐hole on the F atoms of CH3OF is due to the enhancement of the electronegativity of the O atom that participates in the beryllium bond. This atom recovers part of the charge transferred to Be by polarizing the valence density of the F into the bonding region. An analysis of the electron density shows that indeed this bond becomes reinforced, but the F atom becomes more electron deficient with the appearance of the σ‐hole. Importantly, similar effects are also observed even when the atom participating in the beryllium bond is not directly attached to the F atom, as in NO2F, NO3F, or NCF. Hence, whereas the isolated CH3OF, NO2F, and NO3F are unable to yield F⋅⋅⋅Base halogen bonds, their complexes with BeX2derivatives are able to yield such bonds. Significant cooperative effects between the new halogen bond and the beryllium bond reinforce the strength of both noncovalent interactions.
Dehydrogenative TEMPO‐Mediated Formation of Unstable Nitrones: Easy Access to N‐Carbamoyl Isoxazolines
Authors: Gini Andrea , Segler Marwin , Kellner Dominik , Mancheño Olga García
Published: July 2015

N‐carbamoyl nitrones represent an important class of reagents for the synthesis of a variety of natural and biologically active compounds. These compounds are generally converted into valuable 4‐isoxazolines upon cyclization reaction with dipolarophiles. However, these types of N‐protected nitrones are highly unstable, which limits their synthesis, storage and practical use, enforcing alternative lengthy or elaborated synthetic routes. In this work, a 2,2,6,6‐tetramethylpiperidin‐1‐oxyl (TEMPO)‐mediated formal “dehydrogenation” of N‐protected benzyl‐, allyl‐ and alkyl‐substituted hydroxylamines followed by in situ trapping of the generated unstable nitrones into N‐carbamoyl 4‐isoxazolines is presented. A plausible mechanism is also proposed, in which the dipolarophile shows an important assistant role in the generation of the active nitrone intermediate. This simple protocol avoids the problematic isolation of N‐carbamoyl protected nitrones, providing new synthetic possibilities in isoxazoline chemistry.
An Indigo Carmine‐Based Hybrid Nanocomposite with Supramolecular Control of Dye Aggregation and Photobehavior
Authors: Costa Ana L. , Gomes Ana C. , Pillinger Martyn , Gonçalves Isabel S. , de Melo J. Sérgio Seixas
Published: July 2015

Zn‐Al layered double hydroxides (LDHs) containing solely indigo carmine (IC) or 1‐hexanesulfonate (HS) anions, or a mixture of the two with different HS/IC molar ratios, were prepared by the direct synthesis method and characterized by various techniques. Hydrotalcite‐type phases were obtained with basal spacings of 17.6 Å for the LDH intercalated by IC (IC‐LDH) and 18.2–18.3 Å for the other materials containing HS. From the basal spacing for IC‐LDH and UV/Vis spectroscopic data, it is proposed that the dye molecules assemble within the interlayer galleries to form a J‐type stacking arrangement. A comprehensive electronic spectral and photophysical study was undertaken for IC in solution and all materials, aiming to obtain a detailed characterization of the host–guest and guest–guest interactions. In solution (the solvent surrounded “isolated” molecule), IC presents a fast excited state proton transfer with rate constants of ∼1.2–1.4×1011 s−1, which is linked to the very efficient radiationless deactivation channel. In the solid state it is shown that incorporation of IC within the LDH decreases the level of aggregation, and that further addition of HS induces the appearance of isolated IC units within the LDH galleries. The indigo carmine‐based nanocomposites reported constitute a step forward in the design of hybrid materials with tunable properties.
A V‐Shaped Polyaromatic Amphiphile: Solubilization of Various Nanocarbons in Water and Enhanced Photostability
Authors: Kondo Kei , Akita Munetaka , Nakagawa Takafumi , Matsuo Yutaka , Yoshizawa Michito
Published: July 2015

Nanocarbons are synthetic carbon‐rich compounds with polyaromatic frameworks that have lately attracted attention as emerging functional materials. However, their extreme hydrophobicity and aggregation peculiarity, besides their shape and size diversities, precluded their study in solution, especially in “green” water. More convenient and general solubilizing methods of nanocarbon frameworks are required by using non‐covalent supramolecular interactions. Here we report a protocol for solubilizing a wide range of nanocarbons, that is, fullerenes (C60, C70, C84, and C120), polyarenes (tetracene, pentacene, perylene, coronene, and hexabenzocoronene), and carbon nanotubes (single‐walled and multi‐walled CNTs), in water through manual grinding with V‐shaped polyaromatic amphiphiles. The obtained aqueous nanocomposites are composed of nanocarbons encircled by the polyaromatic frameworks of the amphiphiles through multiple aromatic–aromatic interactions. Notably, the encapsulated photosensitive nanocarbons, such as tetracene, pentacene, and fullerene dimer, exhibit unusual stability toward UV/Vis light.
Benzo[c,d]indole‐Containing Aza‐BODIPY Dyes: Asymmetrization‐Induced Solid‐State Emission and Aggregation‐Induced Emission Enhancement as New Properties of a Well‐Known Chromophore
Authors: Shimizu Soji , Murayama Ai , Haruyama Takuya , Iino Taku , Mori Shigeki , Furuta Hiroyuki , Kobayashi Nagao
Published: July 2015

A series of symmetric and asymmetric benzo[c,d]indole‐containing aza boron dipyrromethene (aza‐BODIPY) compounds was synthesized by a titanium tetrachloride‐mediated Schiff‐base formation reaction of commercially available benzo[c,d]indole‐2(1H)‐one and heteroaromatic amines. These aza‐BODIPY analogues show different electronic structures from those of regular aza‐BODIPYs, with hypsochromic shifts of the main absorption compared to their BODIPY counterparts. In addition to the intense fluorescence in solution, asymmetric compounds exhibited solid‐state fluorescence due to significant contribution of the vibronic bands to both absorption and fluorescence as well as reduced fluorescence quenching in the aggregates. Finally, aggregation‐induced emission enhancement, which is rare in BODIPY chromophores, was achieved by introducing a nonconjugated moiety into the core structure.
Three Series of Sulfo‐Functionalized Mixed‐Linker CAU‐10 Analogues: Sorption Properties, Proton Conductivity, and Catalytic Activity
Authors: Reimer Nele , Bueken Bart , Leubner Sebastian , Seidler Christopher , Wark Michael , De Vos Dirk , Stock Norbert
Published: July 2015

Ten mixed‐linker metal–organic frameworks [Al(OH)(m‐BDC‐X)1−y(m‐BDC‐SO3H)y] (H2BDC=1,3‐benzenedicarboxylic acid; X=H, NO2, OH) exhibiting the CAU‐10‐type structure were synthesized. The compounds can be grouped into three series according to the combination of ligands employed. The three series of compounds were obtained by employing different ratios of m‐H2BDC‐X and m‐H2BDC‐SO3Li. The resulting compounds, which are denoted CAU‐10‐H/Sx, ‐N/Sx and ‐O/Sx, show exceptionally high thermal stability for sulfonated materials of up to 350 °C. Detailed characterization with special focus on polarity and acidity was performed, and the impact of the additional SO3H groups is clearly demonstrated by changes in the sorption affinities/capacities towards several gases and water vapor. In addition, selected samples were evaluated for proton conductivity and as catalysts for the gas‐phase dehydration of ethanol to ethylene. While only very low proton conductivities were observed, a pronounced increase in catalytic activity was achieved. Although reactions were performed at temperatures of 250 and 300 °C for more than 40 h, no desulfonation and no loss of crystallinity were observed, and stable ethanol conversion resulted. This demonstrates the high stability of this material.
The Synthesis and Dynamic Structures of Multinuclear Complexes of Large Porphyrinoids Expanded by Phenylene and Thienylene Spacers
Authors: Setsune Jun‐ichiro , Toda Masayuki , Yoshida Takafumi , Imamura Keigo , Watanabe Keigo
Published: July 2015

1,3‐Bis(2‐pyrryl)benzene was used to prepare dibenziamethyrin, in which two pyrrole units of [24]amethyrin(1.0.0.1.0.0) are replaced by benzene. 1,4‐Bis(2‐pyrryl)benzene, 2,5‐bis(2‐pyrryl)thiophene, and 4,4′‐bis(2‐pyrryl)biphenyl were also used in place of 2,2′‐bipyrrole to give expanded analogues of [24]rosarin(1.0.1.0.1.0) and [32]octaphyrin(1.0.1.0.1.0.1.0). These large porphyrinoids can incorporate multiple metal units of Rh(CO)2 and Pd(π‐allyl) with considerable deviation of the metal atoms from the dipyrrin planes, evidenced by X‐ray crystallography. The coordinated Rh(CO)2 group shuttled between both sides of the macrocycle; the rate was dependent on the spacer, ring size, and number of metal atoms. Variable temperature 1H NMR spectroscopy showed that the tris‐rhodium complexes of the expanded rosarins with 1,4‐phenylene or 2,5‐thienylene spacers adopt a C3v‐symmetric form and a Cs‐symmetric form as a result of the Rh(CO)2 groups hopping through the macrocycle cavity. The C3v‐symmetric form has a greater dipole moment and, therefore, is favored in solvents of greater polarity. The Rh(CO)2 groups in the tris‐rhodium complex of the expanded rosarin with 4,4′‐biphenylene spacers hop so fast that an averaged spectral pattern (D3h) was seen in the 1H NMR spectrum, even at −60 °C. Expanded octaphyrins with 1,4‐phenylene and 2,5‐thienylene spacers bind four Rh(CO)2 groups outside the macrocycle cavity to form a D2d‐symmetric saddle‐shaped structure that did not show any dynamic behavior on the NMR timescale, even at 80 °C. This tetranuclear complex is one of the largest porphyrinoid metal complexes characterized by X‐ray crystallography to date.
Synthesis and Thorough Investigation of Discrete Organotin Telluride Clusters
Authors: Eußner Jens P. , Kusche Ralph O. , Dehnen Stefanie
Published: July 2015

Systematic experimental and theoretical investigations of reactions of R1SnCl3 (R1=CMe2CH2C(Me)O) with (Me3Si)2Te allowed for the stepwise formation and single‐crystalline isolation of the first tin sesquitelluride clusters with functional organic ligands. Subsequent derivatization of the latter took place under reorganization of the inorganic core, affording clusters with complex hybrid architectures.