bluuebunny/crossref_metadata_2025 huggingface dataset:
Perineural invasion in pancreatic cancer: proteomic analysis and in vitro modelling
Authors: Alrawashdeh Wasfi , Jones Richard , Dumartin Laurent , Radon Tomasz P. , Cutillas Pedro R. , Feakins Roger M. , Dmitrovic Branko , Demir Ihsan Ekin , Ceyhan Guralp O. , Crnogorac‐Jurcevic Tatjana
Published: January 2019

Perineural invasion (PNI) is a common and characteristic feature of pancreatic ductal adenocarcinoma (PDAC) that is associated with poor prognosis, tumor recurrence, and generation of pain. However, the molecular alterations in cancer cells and nerves within PNI have not previously been comprehensively analyzed. Here, we describe our proteomic analysis of the molecular changes underlying neuro‐epithelial interactions in PNI using liquid chromatography–mass spectrometry (LC‐MS/MS) in microdissected PNI and non‐PNI cancer, as well as in invaded and noninvaded nerves from formalin‐fixed, paraffin‐embedded PDAC tissues. In addition, an in vitro model of PNI was developed using a co‐culture system comprising PDAC cell lines and PC12 cells as the neuronal element. The overall proteomic profiles of PNI and non‐PNI cancer appeared largely similar. In contrast, upon invasion by cancer cells, nerves demonstrated widespread plasticity with a pattern consistent with neuronal injury. The up‐regulation of SCG2 (secretogranin II) and neurosecretory protein VGF (nonacronymic) in invaded nerves in PDAC tissues was further validated using immunohistochemistry. The tested PDAC cell lines were found to be able to induce neuronal plasticity in PC12 cells in our in vitro established co‐culture model. Changes in expression levels of VGF, as well as of two additional proteins previously reported to be overexpressed in PNI, Nestin and Neuromodulin (GAP43), closely recapitulated our proteomic findings in PDAC tissues. Furthermore, induction of VGF, while not necessary for PC12 survival, mediated neurite extension induced by PDAC cell lines. In summary, here we report the proteomic alterations underlying PNI in PDAC and confirm that PDAC cells are able to induce neuronal plasticity. In addition, we describe a novel, simple, and easily adaptable co‐culture model for in vitro study of neuro‐epithelial interactions.
Polypyrrole and Carbon Nanotube Co‐Composited Titania Anodes with Enhanced Sodium Storage Performance in Ether‐Based Electrolyte
Authors: Yang Xuming , Wang Shuo , Zhuang Xuming , Tomanec Ondrej , Zboril Radek , Yu Denis Y. W. , Rogach Andrey L.
Published: January 2019

In terms of applications for sodium‐ion batteries, titania shows several compelling features, such as environmental availability, favorable sodiation potential, and long cycle lifespan, but it also possesses several drawbacks such as the low utilization and low initial coulombic efficiency (ICE). A double‐fold carbon incorporation strategy of improving titania anode materials, namely coating titania nanoparticles with polypyrrole (PPY) and integrating them into a carbon nanotube (CNT) network, is introduced. This treatment not only ensures direct contact of individual titania nanoparticles with the conductive components in the composite but also builds a 3D interconnecting CNT framework to facilitate both mass and charge transfer. The TiO2/PPY/CNT composite delivers reversible capacity of 252 and 201 mAh g−1 at 0.1 and 1 C, respectively; achieves an ICE of 70%, which is the highest value so far, in an ether‐based electrolyte; and retains nearly 80% of its capacity in a 3000‐cycle test. Co‐compositing titania with PPY and CNT guarantees both efficient electrical connection of active materials and resilience against cycling, and this strategy is feasible for various electrode materials which usually need carbon incorporation to improve capacity and stabilize cycling.
Low‐Temperature Growth of Hard Carbon with Graphite Crystal for Sodium‐Ion Storage with High Initial Coulombic Efficiency: A General Method
Authors: Zhao Xun , Ding Yuan , Xu Qi , Yu Xiao , Liu Yong , Shen Hui
Published: January 2019

Practical application of hard carbon materials in sodium‐ion batteries (SIBs) is largely limited by their low initial coulombic efficiency (ICE), which may be improved by increasing the graphitization degree. However, biomass‐derived hard carbon is usually nongraphitizable and extremely difficult to graphitize by direct heating even at 3000 °C. Herein, a general strategy is reported for fabricating hard carbon materials with graphite crystals at 1300 °C promoted by external graphite that serves as a crystal template for the growth of graphite crystals. The graphite crystals enable the contacted pseudographitic domains with a high‐level ordered structure, large domain size, and low defects, leading to an enhanced ICE. The obtained hard carbon materials with graphite crystals, using the carbonized eggshell membranes, and sucrose‐derived microsphere as precursors, achieve very high ICE of 89% and 91% with reversible capacity of 310 and 301 mA h g−1, respectively. Therefore, using external graphite to promote high‐level ordering pseudographitic domains at low temperature is quite useful to improve ICE for SIB applications.
15% Efficiency Tandem Organic Solar Cell Based on a Novel Highly Efficient Wide‐Bandgap Nonfullerene Acceptor with Low Energy Loss
Authors: Liu Gongchu , Jia Jianchao , Zhang Kai , Jia Xiao'e , Yin Qingwu , Zhong Wenkai , Li Li , Huang Fei , Cao Yong
Published: January 2019

A tandem organic solar cell (OSC) is a valid structure to widen the photon response range and suppress the transmission loss and thermalization loss. In the past few years, the development of low‐bandgap materials with broad absorption in long‐wavelength region for back subcells has attracted considerable attention. However, wide‐bandgap materials for front cells that have both high short‐circuit current density (JSC) and open‐circuit voltage (VOC) are scarce. In this work, a new fluorine‐substituted wide‐bandgap small molecule nonfullerene acceptor TfIF‐4FIC is reported, which has an optical bandgap of 1.61 eV. When PBDB‐T‐2F is selected as the donor, the device offers an extremely high VOC of 0.98 V, a high JSC of 17.6 mA cm−2, and a power conversion efficiency of 13.1%. This is the best performing acceptor with such a wide bandgap. More importantly, the energy loss in this combination is 0.63 eV. These properties ensure that PBDB‐T‐2F:TfIF‐4FIC is an ideal candidate for the fabrication of tandem OSCs. When PBDB‐T‐2F:TfIF‐4FIC and PTB7‐Th:PCDTBT:IEICO‐4F are used as the front cell and the back cell to construct tandem solar cells, a PCE of 15% is obtained, which is one of best results reported to date in the field of organic solar cells.
Comparison of the long‐term outcomes of the self‐expandable metallic stent and transanal decompression tube for obstructive colorectal cancer
Authors: Sato Ryuichiro , Oikawa Masaya , Kakita Tetsuya , Okada Takaho , Oyama Atsushi , Abe Tomoya , Yazawa Takashi , Tsuchiya Haruyuki , Akazawa Naoya , Ohira Tetsuya , Harada Yoshihiro , Tanaka Megumi , Okano Haruka , Ito Kei , Tsuchiya Takashi
Published: January 2019

Aim

Endoscopic decompression using the self‐expandable metallic colonic stent (SEMS) or transanal decompression tube (TDT) can convert emergency surgery into elective one‐stage surgery for obstructive colorectal cancer (OCRC). The aim of the present study was to clarify the effect of SEMS and TDT on long‐term oncological outcomes.

Methods

We retrospectively analyzed 76 consecutive pathological stage II and III OCRC patients who were inserted with SEMS or TDT as a bridge to curative surgery between 2009 and 2018.

Results

There were 53 SEMS cases and 23 TDT cases. The tumor was located in the left colon in 58 cases and in the right colon in 18 cases. The interval between the decompression and the surgery was 16.5 days in the SEMS group and 13.0 days in the TDT group (P = 0.09). Technical and clinical success rates were 100% and 100% for SEMS, and 95% and 91% for TDT, respectively. Stoma was created in four patients in the SEMS group, and in five in the TDT group (P = 0.08). Three‐year overall survival rates of the SEMS and TDT groups were 82% and 86% (P = 0.94), and disease‐free survival rates were 68% and 62% (P = 0.79), respectively. The recurrence pattern was not significantly different.

Conclusion

This study found no statistically significant differences between the effects of SEMS and TDT for OCRC as a bridge to surgery on long‐term outcomes.
Tin‐Mediated One‐Pot Preparation of β‐Trifluoromethyl‐β‐ acylhydrazonyl Carbonyl Compounds
Authors: Wang Ke‐Hu , Shi Baobao , Wang Yalin , Wang Jianglong , Huang Danfeng , Su Yingpeng , Hu Yulai
Published: January 2019

A concise and efficient protocol for the preparation of β‐trifluoromethyl‐β‐acylhydrazonyl carbonyl compounds was developed from multicomponent one‐pot reactions of trifluoroacetaldehyde methyl hemiacetal, acylhydrazines and 2‐bromocarbonyl compounds in the presence of tin powder. The reactions can be carried out under mild reaction conditions to give the products in good to excellent yields.
A randomized study of solriamfetol for excessive sleepiness in narcolepsy
Authors: Thorpy Michael J. , Shapiro Colin , Mayer Geert , Corser Bruce C. , Emsellem Helene , Plazzi Giuseppe , Chen Dan , Carter Lawrence P. , Wang Hao , Lu Yuan , Black Jed , Dauvilliers Yves
Published: January 2019

Objective

Solriamfetol (JZP‐110) is a selective dopamine and norepinephrine reuptake inhibitor with wake‐promoting effects. This phase 3 study (NCT02348593) evaluated the safety and efficacy of solriamfetol in narcolepsy.

Methods

Patients with narcolepsy with mean sleep latency <25 minutes on the Maintenance of Wakefulness Test (MWT), Epworth Sleepiness Scale (ESS) score ≥10, and usual nightly sleep ≥6 hours were randomized to solriamfetol 75, 150, or 300 mg, or placebo for 12 weeks. Coprimary endpoints were change from baseline to week 12 in MWT and ESS. Improvement on the Patient Global Impression of Change (PGI‐C) was the key secondary endpoint.

Results

Safety and modified intention‐to‐treat populations included 236 and 231 patients, respectively. Solriamfetol 300 and 150 mg were positive on both coprimary endpoints. Least squares mean (standard error [SE]) changes from baseline were 12.3 (SE = 1.4) and 9.8 (SE = 1.3) minutes for solriamfetol 300 and 150 mg on the MWT, respectively, versus 2.1 (SE = 1.3) minutes for placebo, and −6.4 (SE = 0.7) for 300 mg and −5.4 (SE = 0.7) for 150 mg on the ESS versus −1.6 (SE = 0.7) for placebo (all p < 0.0001). At week 12, higher percentages of patients treated with solriamfetol 150 mg (78.2%) and 300 mg (84.7%) reported PGI‐C improvement relative to placebo (39.7%; both p < 0.0001). Adverse events ≥5% across all solriamfetol doses included headache (21.5%), nausea (10.7%), decreased appetite (10.7%), nasopharyngitis (9.0%), dry mouth (7.3%), and anxiety (5.1%).

Interpretation

Solriamfetol has the potential to be an important therapeutic option for the treatment of impaired wakefulness and excessive sleepiness in patients with narcolepsy. ANN NEUROL 2019;85:359–370.
Catalytic and biological valorization of a supramolecular mononuclear copper complex based 4‐aminopyridine
Authors: Hfidhi Nabil , bkhairia Intidhar , Atoui Dhieb , Boonmak Jaursup , Nasri Moncef , Ben Salem Ridha , Youngme Sujittra , Naïli Houcine
Published: January 2019

Hydrothermal reaction of copper bromide with 4‐aminopyridine in DMF solution yields a new mononuclear copper complex [Cu(C5H6N2)4]2Br.2(C3H7NO) abbreviated Cu‐4AP‐Br. The product was characterized, structurally, by single‐crystal X‐ray diffraction analysis and, thermally, by DSC‐ATG measurement. The inorganic–organic hybrid compound Cu‐4AP‐Br crystallizes in the centrosymmetric space group Pbcn, exhibiting a supramolecular network. Simultaneous DSC‐ATG analysis shows that this compound remains stable up to 100 °C and then performs a successive decompositions accompanied with endothermic peaks. The complex Cu‐4AP‐Br was applied as a catalyst in the Heck coupling reaction under ultrasonic irradiation in various reaction conditions. The yields, obtained for a short period of time, allow us to consider this complex, generating selectivity on the external position of styrene with a preference of the trans form over cis, as an excellent catalyst for this type of reaction. Interestingly, Cu‐4AP‐Br displayed important antibacterial (Gram‐positive and Gram‐negative) and antioxidant activities (β‐carotene bleaching inhibition, scavenging effect on DPPH free radical, and reducing power).
OR Time and Sacral Pressure Injuries in Critically Ill Surgical Patients
Authors: Grap Mary Jo , Schubert Christine M. , Munro Cindy L. , Wetzel Paul A. , Burk Ruth S. , Lucas Valentina , Pepperl Anathea
Published: January 2019

Critically ill patients are at risk for developing pressure injuries during operative and other invasive procedures. The purpose of this secondary analysis was to explore the relationship of OR time to sacral pressure injuries in critically ill patients using high frequency ultrasound as a method of assessment. The 41 participants examined in this study had both time in the OR and up to eight days of pressure injury data. The multivariable model containing OR bed time, body mass index, and Braden Scale score produced the best prediction of pressure injury (area under the curve = 0.859). A higher body mass index (P = .09), shorter OR bed time (P = .01), and lower Braden Scale score (P = .05) were associated with a greater chance of pressure injury. These results suggest that use of high frequency ultrasound may identify tissue changes before observable skin changes, leading to earlier pressure injury prevention strategies.
Novel approach to promote the hydrophobic association: Introduction of short alkyl chains into hydrophobically associating polyelectrolytes
Authors: Han Yuhao , Tan Jiawen , Wang Dongping , Xu Kun , An Huiyong
Published: January 2019

A novel approach to promote hydrophobic association by incorporating short alkyl chains onto polyelectrolytes (HAPEs) was presented. A series of HAPEs was synthesized by free radical copolymerization in aqueous media with acrylamide (AM), 11‐acrylamidoundecanoic acid (C11AM), and 6‐acrylamidohexanoic acid (C6AM). The structures and compositions of the polymers were confirmed by 1H‐NMR, and the molecular weights were determined by GPC. Results of rheological experiments revealed that viscosities increased greatly in samples containing C11AM and C6AM compared with the sample without C6AM. The sample without C6AM was also characterized by critical association concentrations and critical angular frequencies. Solubilization and bridging interaction were considered as the possible reasons. Pyrene fluorescence probe data and 1H‐NMR spin–spin relaxation times further illustrated the reinforcement of hydrophobic associations by short alkyl side chains. All the results showed that the optimum content of C6AM was 1 mol % in the prepared HAPEs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47581.
Enzyme production by solid‐state fermentation on soybean meal: A comparative study of conventional and ultrasound‐assisted extraction methods
Authors: Salim Abdalla Ali , Grbavčić Sanja , Šekuljica Nataša , Vukašinović‐Sekulić Maja , Jovanović Jelena , Jakovetić Tanasković Sonja , Luković Nevena , Knežević‐Jugović Zorica
Published: January 2019

Protease, cellulase, and α‐amylase producing Bacillus subtilis strain was cultivated by solid‐state fermentation technique using soybean meal as a substrate. The aim of the present study was to establish a highly efficient enzymes’ extraction method as a first stage in downstream processing. The conventional extraction procedure was optimized by determining pH, stirring rate, solid/liquid ratio, and time of extraction on enzymes’ recoveries from fermented soybean meal. Yields of leached enzymes were compared to the amounts of enzymes that are achieved with ultrasound‐assisted extraction (UAE). UAE was established to be superior method for obtaining higher yields of proteases (up to 330 IU) and α‐amylases (825 IU), under significantly shorter extraction time and gaining more concentrated product. However, the obtained model predicts that conventional process led to a product with a higher cellulolytic activity (≥7.5 IU).
Electrochemiluminescent functional nucleic acids‐based sensors for food analysis
Authors: Xu Huifeng , Zhu Xi , Wang Jian , Lin Zhenyu , Chen Guonan
Published: January 2019

Foodborne contaminants widely exist in foods, which can lead to various foodborne diseases and food safety issues. The development of quick, sensitive and universal analytical approaches for foodborne contaminants is imperative. Electrochemiluminescent functional nucleic acids (ECL FNAs)‐based sensors are a series of sensing devices using FNAs as the recognition elements and ECL as the transducer. Contributing to the specific recognition ability of FNA and the high sensitivity of ECL, ECL FNA‐based sensors are considered to be of great application potential for foodborne contaminants monitoring. This review mainly presents the applications of ECL FNA‐based sensors for foodborne contaminants (including microorganisms, mycotoxins, allergens, antibiotics, heavy metal ions, pesticides and some illegal additives). In general, the application of ECL FNA‐based sensors in the field of food analysis is just in its infancy. Although there are several limitations and challenges, it is envisaged that ECL FNA‐based sensors will have broad prospects for food analysis in the future.
Human T lymphotropic virus type 1 and risk of cardiovascular disease: High‐density lipoprotein dysfunction versus serum HDL‐C concentrations
Authors: Samadi Sara , Abolbashari Samaneh , Meshkat Zahra , Mohammadpour Amir Hooshang , Kelesidis Theodoros , Gholoobi Aida , Mehramiz Mehrane , Tabadkani Mahla , Sadabadi Fatemeh , Dalirfardouei Razieh , Ferns Gordon A , Ghayour‐Mobarhan Majid , Avan Amir
Published: January 2019

High‐density lipoprotein (HDL) is thought to be protective against cardiovascular disease (CVD), and HDL dysfunction is considered to be a risk factor for CVD. It is unclear whether there is an association between Human T lymphotropic virus type 1 (HTLV1) infection and CVD risk. We have assessed HDL lipid peroxidation (HDLox) as a marker of HDL dysfunction and CVD risk in a subgroup of the MASHAD cohort study. One hundred and sixty two individuals including 50 subjects positive for HTLV1 infection and 112 individuals negative for HTLV1 infection were recruited. Anthropometric and biochemical parameters including serum hs‐CRP, fasted lipid profile (HDL‐C, LDL, triglycerides, and cholesterol), and fasting blood glucose were determined. Serum HDLox was also measured in the study participants. Multivariate analyses were used to evaluate the association between serum HDLox and HTLV1 infection. None of the traditional CVD risk factors were associated with HTLV1 infection, including serum HDL‐C. However, serum HDLox was independently associated with the presence of HTLV1 infection. Logistic regression analysis showed that subjects who were positive for HTLV1 infection were also significantly more likely than uninfected individuals to have higher HDLox (odds ratio 9.35, 95%CI: 3.5–24.7; P < 0.001). HDLox was increased approximately 20% (P < 0.001) in infected subjects compared to the uninfected group. Serum HDLox is a marker of CVD risk factor and increased in individuals affected by HTLV1 infection compared to healthy subjects. © 2019 BioFactors, 45(3):374–380, 2019
Complementary Chromophore Decoration in NU‐1000 via Solvent‐Assisted Ligands Incorporation: Efficient Energy Transfer within the Metal‐Organic Frameworks
Authors: Oh Jung Suk , Park Kyoung Chul , Gupta Gajendra , Lee Chang Yeon
Published: January 2019

BODIPY‐incorporated solvent‐assisted ligand incorporation metal‐organic frameworks (SALI‐MOFs) were designed and synthesized using NU‐1000 and carboxylic acid functionalized BODIPY moieties by the solvent‐assisted ligand incorporation (SALI) approach. SALI‐MOFs were characterized by various technique including powder X‐ray diffraction, scanning electron microscope, N2 adsorption/desorption isotherms, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy. The SALI‐MOFs were found to have cooperative light‐harvesting properties and shown to possess efficient singlet oxygen (1O2) generation ability.
The preoperative neutrophil‐to‐lymphocyte ratio is not a marker of prostate cancer characteristics but is an independent predictor of biochemical recurrence in patients receiving radical prostatectomy
Authors: Cao Zhi , Ji Jin , Zhang Chao , Wang Fubo , Xu Huan , Yu Yongwei , Sun Yinghao
Published: January 2019

The neutrophil‐to‐lymphocyte ratio (NLR) has been reported to be a prognostic marker in prostate cancer. In this study, we assessed the association between preoperative NLR and the clinicopathological characteristics, biomolecular features and prognosis of patients with localized prostate cancer treated with radical prostatectomy. A total of 994 subjects were retrospectively enrolled, and the histological specimens of 210 patients were retrieved for constructing a tissue microarray. Immunohistochemistry was then performed to assess the expression of AR, ERG, PTEN, p‐AKT, Bcl‐2, Beclin‐1, Ki‐67, CD3, CD4, CD8, IFN‐γ and TNF‐α. No significant differences in the NLR distributions among clinicopathological variables were observed (P > 0.05) when the original NLR data were utilized. When we dichotomized the NLR value into the high‐NLR group (NLR ≥ 2) and low‐NLR group (NLR < 2), we found that the patients in the high‐NLR group had more prostate capsule invasion (P = 0.047). Additionally, no significant correlation was found between the NLR and infiltrating CD3+ cells, the CD4/CD8 ratio, AR, ERG, PTEN, p‐AKT, Bcl‐2, Beclin‐1, Ki‐67, IFN‐γ or TNF‐α (P > 0.05). When we analyzed the data of patients without postoperative adjuvant hormone therapy or radiotherapy, univariate and multivariate survival analysis indicated that a high NLR was a predictor of better BCR‐free survival (P < 0.05). When analyzing the entire cohort, univariate survival analysis showed that the high‐NLR group had significantly poorer overall survival (P < 0.05). In conclusion, NLR cannot reflect prostate cancer characteristics or the local immune microenvironment, but a high NLR can serve as an independent predictor of better BCR.
Long‐term survival outcome with tyrosine kinase inhibitors and surgical intervention in patients with metastatic or recurrent gastrointestinal stromal tumors: A 14‐year, single‐center experience
Authors: Kim Jwa Hoon , Ryu Min‐Hee , Yoo Changhoon , Chae Heejung , Na Hana , Beck Moyoul , Kim Beom Su , Yoo Moon‐Won , Yook Jeong Hwan , Kim Byung Sik , Kim Ki‐Hun , Kim Chan Wook , Kang Yoon‐Koo
Published: January 2019

The long‐term effects of tyrosine kinase inhibitors (TKIs), including imatinib, and surgical intervention on advanced gastrointestinal stromal tumor (GIST) were evaluated. All 379 patients had metastatic or recurrent GIST and started 400 mg/d imatinib at the Asan Medical Center in periods 1 and 2 [2001‐2007 (33.2%) and 2008‐2014 (66.8%), respectively]. Men constituted 60.4%; median patient age and tumor size at the initiation of imatinib were 58.6 (14.6‐85.5) years and 51 (0‐324) mm, respectively, without differences between periods except for older age and less preimatinib surgery in period 2. Response and disease control rates with imatinib in measurable GIST were 63.1% and 94.3%, respectively, without differences between periods. More patients in period 2 underwent surgical resection for TKI‐responsive diseases within the first 2 years (24.9%, P = 0.006). With a median follow‐up of 6.1 years (2.5‐16.0) in survivors, median progression‐free survival (PFS) was 5.4 years [95% confidence interval (CI), 4.0‐6.9]. Subsequent sunitinib (P = 0.066) and regorafenib (P = 0.003) were more commonly administered in period 2. Median overall survival (OS) was 8.8 years (95% CI, 7.8‐9.7). PFS with imatinib (P = 0.002) and OS (P = 0.019) were significantly longer in period 2. Young age, smaller tumor size at the initiation of imatinib, KIT exon 11 mutation, surgical intervention, and period 2 were favorable factors for PFS and OS. Patients with advanced GIST showed better prognosis with the optimal use of imatinib, along with active surgical intervention and more common use of subsequent TKIs in period 2.
Orthogonally Stimulated Assembly/Disassembly of Depsipeptides by Rational Chemical Design
Authors: Pieszka Michaela , Sobota Adriana Maria , Gačanin Jasmina , Weil Tanja , Ng David Y. W.
Published: January 2019

Controlling the assembly and disassembly of cross‐β‐sheet‐forming peptides is one of the predominant challenges for this class of supramolecular material. As they constitute a continuously propagating material, every atomic change can be exploited to bring about distinct responses at the architectural level. We report herein that, by using rational chemical design, serine and methionine can both be used as orthogonal chemical triggers to signal assembly/disassembly through their corresponding stimuli. Serine is used to construct an ester‐bond oligopeptide that can undergo O,N‐acyl rearrangement, whereas methionine is sensitive to oxidation by H2O2. Using the example peptide sequence, KIKISQINM, we demonstrate that assembly and disassembly can be independently controlled on demand.
On the Limited Role of Electronic Support Effects in Selective Alkyne Hydrogenation: A Kinetic Study of Au/MOx Catalysts Prepared from Oleylamine‐Capped Colloidal Nanoparticles
Authors: Bruno James E. , Sravan Kumar K. B. , Dwarica Nicolas S. , Hüther Alexander , Chen Zhifeng , Guzman Clemente S. , Hand Emily R. , Moore William C. , Rioux Robert M. , Grabow Lars C. , Chandler Bert D.
Published: January 2019

We report a quantitative kinetic evaluation and study of support effects for partial alkyne hydrogenation using oleylamine‐capped Au colloids as catalyst precursors. The amine capping agents can be removed under reducing conditions, generating supported Au nanoparticles of ∼2.5 nm in diameter. The catalysts showed high alkene selectivity (>90 %) at all conversions during alkyne partial hydrogenation. Catalytic activity, observed rate constants, and apparent activation energies (25–40 kJ/mol) were similar for all Au catalysts, indicating support effects are relatively small. Alkyne adsorption, probed with FTIR and DFT, showed adsorption on the support was associated with hydrogen‐bonding interactions. DFT calculations indicate strong alkyne adsorption on Au sites, with the strongest adsorption sites at the metal‐support interface (MSI). The catalysts had similar hydrogen reaction orders (0.7–0.9), and 1‐octyne reaction orders (∼−0.2), suggesting a common mechanism. The reaction kinetics are most consistent with a mechanism involving the non‐competitive activated adsorption of H2 on an alkyne‐covered Au surface.
Intercalating MnO2 Nanosheets With Transition Metal Cations to Enhance Oxygen Evolution
Authors: Yang Yue , Su Xingsong , Zhang Lei , Kerns Peter , Achola Laura , Hayes Veronica , Quardokus Rebecca , Suib Steven L. , He Jie
Published: January 2019

The catalytic activity of MnO2 nanosheets towards oxygen evolution depends highly on their interlayer environment. We present a systematic investigation on fine‐tuning of the interlayer environment of MnO2 nanosheets by intercalation through a facile cation exchange with inexpensive first‐row transition metal cations, including Ni2+, Co2+, Cu2+, Zn2+, and Fe3+ ions. Among them, the Ni‐intercalated MnO2 nanosheets show remarkably enhanced OER activity and long‐term stability, compared to pristine MnO2 nanosheets. The overpotential of 330 mV at a current density of 10 mA cm−2 is observed for the Ni‐intercalated MnO2 nanosheets. The ehancement mechanism of OER is studied by comparing physiochemical properties, such as the oxidation state of Mn, the interlayer distance, the increase in the disorder/twisting of MnO6 octahedra, and the interlayer cooperative binding of water molecules. The Ni intercalation, different from other metal cations, strengthens the Mn−O bond perpendicularly to the layer chains to facilitate the interlayer catalysis possibly between two Mn sites, and thus promotes the efficiency of oxygen evolution.
Carbon with Surface‐Enriched Nitrogen and Sulfur Supported Au Catalysts for Acetylene Hydrochlorination
Authors: Wang Bolin , Zhao Jia , Yue Yuxue , Sheng Gangfeng , Lai Huixia , Rui Jiayao , He Haihua , Hu Zhongting , Feng Feng , Zhang Qunfeng , Guo Lingling , Li Xiaonian
Published: January 2019

The front cover artwork for Issue 03/2019 is provided by researchers from Industrial Catalysis Institute, Laboratory Breeding Base of Green Chemistry‐Synthesis Technology, Zhejiang University of Technology (P. R. China). The image shows carbon with surface‐enriched nitrogen and sulfur supported Au catalysts for acetylene hydrochlorination. The sulfur species on the carbon surface was considered to be able to selective formation of pyrrolic nitrogen against pyridinic nitrogen, which significantly influence the catalytic performance of Au‐based catalysts.. See the Full Paper itself at https://doi.org/10.1002/cctc.201801555.
Activated Carbon‐Supported Mo‐Co‐K Sulfide Catalysts for Synthesizing Higher Alcohols from CO2
Authors: Liu Su , Zhou Haibo , Zhang Lin , Ma Zhen , Wang Yangdong
Published: January 2019

Activated carbon‐supported Mo‐Co‐K sulfide catalysts, prepared by stepwise impregnation, were used in the synthesis of higher alcohols via CO2 hydrogenation. The catalysts with varying Mo contents and defined K/Mo and Co/Mo molar ratios exhibited relatively high CO2 conversions and high selectivity to total alcohols and C2+ alcohols. Moreover, the influence of calcination conditions on the sulfidation states and catalytic performance was studied. The surface sulfur runoff of the supported catalysts can be effectively suppressed by online calcination. As a result, the selectivity to total alcohols and C2+ alcohols can be improved.
What the Combustion Engineer Gains from CFD Modeling: Gas Furnace
Authors: Hájek Jiří , Vondál Jiří , Juřena Tomáš , Sláma Jaroslav
Published: January 2019

Combustion engineers require correct predictions of trends, especially in cases when computational fluid dynamics is applied for troubleshooting, scale‐up, or decision support in the design phase. Validation of models by parametric studies and in a large‐scale furnace is rare and much needed. This is the primary objective of this work. Similarly, combustion engineers require the prediction of heat loads in specific parts of a boiler or furnace. The second objective of this work is to provide exactly such type of validation for a megawatt‐scale burner. Both cases use natural gas fuel. The models applied to perform the predictions are typical of practicing combustion engineers, providing fast turnaround times. The results provide a perspective on the performance of models serving as workhorses in engineering companies.
Effects of Graphene Quality on Lithium Storage Performances of Fe3O4/Thermally Reduced Graphene Oxide Hybrid Anodes
Authors: Chang Wei , Qu Jin , Hao Shu‐Meng , Zhang Yu‐Jiao , Jiang Zhi‐Guo , Yu Zhong‐Zhen
Published: January 2019

Till now, there are no systematic reports on the effect of the quality of thermally reduced graphene oxide (TRG) on lithium storage properties, as the reported methods to fabricate graphene‐based electrodes are usually not effective enough to reduce graphene oxides to graphene. Herein, graphite oxide is thermally exfoliated and annealed with a high‐temperature graphitization oven at different temperatures (800–2000 °C). A series of Fe3O4/TRG hybrids are synthesized as anode materials for lithium‐ion batteries with TRGs acting as substrates of in‐situ formed Fe3O4 nanoparticles. Both, the electroconductivity of the TRGs and their interfacial interaction with Fe3O4 influence the lithium storage performances of the hybrids. However, the electroconductivity of the TRGs and the formation of interfacial bonds are conflicting. Because the oxygen‐containing groups and defects of TRG are greatly removed leading to enhanced electrical conductivity with the increase of thermal annealing temperature. Hence, the resulting Fe3O4/TRG hybrids show first decreased then increased electrochemical performances with increasing annealed temperatures. In a word, the effect of interfacial interaction is dominant at a relatively low annealing temperature, while the effect of conductivity is dominant at a relatively high annealing temperature. The optimized hybrids exhibit excellent cycling and rate performances. This work should provide useful information for the rational design and construction of high‐performance electrodes for energy storage applications.
Palladium(0)‐Catalyzed Intermolecular Asymmetric Cascade Dearomatization Reaction of Indoles with Propargyl Carbonate
Authors: Ding Lu , Gao Run‐Duo , You Shu‐Li
Published: January 2019

An intermolecular asymmetric cascade dearomatization reaction of indole derivatives with propargyl carbonate was developed. The challenges associated with both the chemoselectivity between the carbon and nitrogen nucleophile and the enantioselective control during the formation of an all‐carbon quaternary stereogenic center were well addressed by a Pd catalytic system derived from the Feringa ligand. A series of enantioenriched multiply substituted fused indolenines were provided in good yields (71–86 %) with excellent enantioselectivity (91–96 % ee) and chemoselectivity (3/4>19:1 in most cases).
Preparation and characterization of a new open‐tubular capillary column for enantioseparation by capillary electrochromatography
Authors: Li Yingjie , Tang Yimin , Qin Shili , Li Xue , Dai Qiang , Gao Lidi
Published: January 2019

In order to use the enantioseparation capability of cationic cyclodextrin and to combine the advantages of capillary electrochromatography (CEC) with open‐tubular (OT) column, in this study, a new OT‐CEC, coated with cationic cyclodextrin (1‐allylimidazolium‐β‐cyclodextrin [AI‐β‐CD]) as chiral stationary phase (CSP), was prepared and applied for enantioseparation. Synthesized AI‐β‐CD was characterized by infrared (IR) spectrometry and mass spectrometry (MS). The preparation conditions for the AI‐β‐CD‐coated column were optimized with the orthogonal experiment design L9(34). The column prepared was characterized by scanning electron microscopy (SEM) and elemental analysis (EA). The results showed that the thickness of stationary phase in the inner surface of the AI‐β‐CD‐coated columns was about 0.2 to 0.5 μm. The AI‐β‐CD content in stationary phase based on the EA was approximately 2.77 mmol·m−2. The AI‐β‐CD‐coated columns could separate all 14 chiral compounds (histidine, lysine, arginine, glutamate, aspartic acid, cysteine, serine, valine, isoleucine, phenylalanine, salbutamol, atenolol, ibuprofen, and napropamide) successfully in the study and exhibit excellent reproducibility and stability. We propose that the column, coated with AI‐β‐CD, has a great potential for enantioseparation in OT‐CEC.
New Cyclams and Their Copper(II) and Iron(III) Complexes: Synthesis and Potential Application as Anticancer Agents
Authors: Pilon Adhan , Lorenzo Julia , Rodriguez‐Calado Sergi , Adão Pedro , Martins Ana M. , Valente Andreia , Alves Luis G.
Published: January 2019

New cyclam derivatives (HOCH2CH2CH2)2(PhCH2)2Cyclam and (HOCH2CH2CH2)2(
PhCH2)2Cyclam, as well as their CuII and FeIII complexes, were synthesized and characterized and their stability in cellular media was assessed. The cytotoxic effect of all compounds was examined on human cervical cancer (HeLa) cells, revealing strong anticancer activity. After 24 h, only complexes with the (HOCH2CH2CH2)2(
PhCH2)2Cyclam ligand are cytotoxic, whereas after incubation for 72 h all compounds show significant antiproliferative effects. Notably, compounds containing
PhCH2 pendant arms on the cyclam ring revealed the most activity, with cytotoxicity values up to 12 times higher than those of cisplatin. All metal complexes seem to induce cell death through the formation of reactive oxygen species.
The role of autologous stem cell transplantation in patients with nodal peripheral T‐cell lymphomas in first complete remission: Report from COMPLETE, a prospective, multicenter cohort study
Authors: Park Steven I. , Horwitz Steven M. , Foss Francine M. , Pinter‐Brown Lauren C. , Carson Kenneth R. , Rosen Steven T. , Pro Barbara , Hsi Eric D. , Federico Massimo , Gisselbrecht Christian , Schwartz Marc , Bellm Lisa A. , Acosta Mark , Advani Ranjana H. , Feldman Tatyana , Lechowicz Mary Jo , Smith Sonali M. , Lansigan Frederick , Tulpule Anil , Craig Michael D. , Greer John P. , Kahl Brad S. , Leach Joseph W. , Morganstein Neil , Casulo Carla , Shustov Andrei R. ,   for the COMPLETE Investigators
Published: January 2019

Background

The role of autologous stem cell transplantation (ASCT) in the first complete remission (CR1) of peripheral T‐cell lymphomas (PTCLs) is not well defined. This study analyzed the impact of ASCT on the clinical outcomes of patients with newly diagnosed PTCL in CR1.

Methods

Patients with newly diagnosed, histologically confirmed, aggressive PTCL were prospectively enrolled into the Comprehensive Oncology Measures for Peripheral T‐Cell Lymphoma Treatment (COMPLETE) study, and those in CR1 were included in this analysis.

Results

Two hundred thirteen patients with PTCL achieved CR1, and 119 patients with nodal PTCL, defined as anaplastic lymphoma kinase–negative anaplastic large cell lymphoma, angioimmunoblastic T‐cell lymphoma (AITL), or PTCL not otherwise specified, were identified. Eighty‐three patients did not undergo ASCT, whereas 36 underwent consolidative ASCT in CR1. At the median follow‐up of 2.8 years, the median overall survival was not reached for the entire cohort of patients who underwent ASCT, whereas it was 57.6 months for those not receiving ASCT (P = .06). ASCT was associated with superior survival for patients with advanced‐stage disease or intermediate‐to‐high International Prognostic Index scores. ASCT significantly improved overall and progression‐free survival for patients with AITL but not for patients with other PTCL subtypes. In a multivariable analysis, ASCT was independently associated with improved survival (hazard ratio, 0.37; 95% confidence interval, 0.15‐0.89).

Conclusions

This is the first large prospective cohort study directly comparing the survival outcomes of patients with nodal PTCL in CR1 with or without consolidative ASCT. ASCT may provide a benefit in specific clinical scenarios, but the broader applicability of this strategy should be determined in prospective, randomized trials. These results provide a platform for designing future studies of previously untreated PTCL.
A randomized trial of immediate versus delayed survivorship care plan receipt on patient satisfaction and knowledge of diagnosis and treatment
Authors: Tevaarwerk Amye J. , Hocking William G. , Buhr Kevin A. , Gribble Mindy , Seaborne Lori A. , Wisinski Kari B. , Burkard Mark E. , Yen Thomas , Wiegmann Douglas A. , Sesto Mary E.
Published: January 2019

Background

Survivorship care plans (SCPs) and care‐planning sessions have been recommended for over a decade, yet evidence for their benefit remains mixed. In a randomized trial, changes in survivor knowledge and satisfaction before and after the receipt of an SCP were assessed.

Methods

Patients with breast cancer who had completed curative‐intent treatment were randomized to immediate versus delayed receipt of an individualized SCP. All participants completed the modified Wisconsin Survey of Cancer Diagnosis and Management in Breast Cancer and the Preparing for Life As a New Survivor survey to assess individual knowledge about cancer diagnosis, treatment, side effects, and follow‐up as well as satisfaction with communication and care coordination. Surveys were completed at baseline, at 4 weeks (before delayed receipt), and again at 12 weeks (after all participants had received SCPs); the primary outcome was change in knowledge at 4 weeks.

Results

In total, 127 eligible women were randomized. An improvement in individual knowledge was observed between baseline and week 12 for both arms combined (+1.6; 95% confidence interval, 0.9‐2.3; P < .001). There was no statistically significant difference in the change in knowledge from baseline through week 4 between the arms. No significant change occurred for satisfaction scores over time.

Conclusions

This randomized trial of immediate versus delayed SCP receipt demonstrated a small improvement (4%) in survivor knowledge. However, this improvement did not appear to be related to SCP provision. The authors hypothesized that the improvement was because of repeated administration of the knowledge survey. If improved survivor knowledge is a goal, then strategies beyond the 1‐time provision and review of an SCP should be explored.
Accurate Monte Carlo simulation of frequency‐domain optical coherence tomography
Authors: Wang Yan , Bai Li
Published: January 2019

Optical coherence tomography (OCT) relies on optical interferometry to provide noninvasive imaging of living tissues. In addition to its 3D imaging capacity for medical diagnosis, its potential use for recovering optical parameters of biological tissues for biological and pathological analyses has also been explored by researchers, as pathological changes in tissue alter the microstructure of the tissue and therefore its optical properties. We aim to develop a new approach to OCT data analysis by estimating optical properties of tissues from OCT scans, which are invisible in the scans. This is an inverse problem. Solving an inverse problem involves a forward modeling step to simulate OCT scans of the tissues with hypothesized optical parameter values and an inverse step to estimate the real optical par1meters values by matching the simulated scans to real scans. In this paper, we present a Monte Carlo (MC)–based approach for simulating the frequency‐domain OCT. We incorporated a focusing Gaussian light beam rather than an infinitesimally thin light beam for accurate simulations. A new and more accurate photon detection scheme is also implemented. We compare our MC model to an analytical OCT model based on the extended Huygens‐Fresnel principle (EHF) to demonstrate the consistency between the two models. We show that the two models are in good agreement for tissues with high scattering and high anisotropy factors.
Fluorescent Canthin‐6‐one Alkaloids from Simaba bahiensis: Isolation, Identification, and Cell‐Labeling Properties
Authors: dos Santos Costa Rafael , do Espírito‐Santo Renan Fernandes , Abreu Lucas Silva , de Oliveira Aguiar Leonardo , Leite Fontes Dara , Fechine Tavares Josean , Sobral da Silva Marcelo , Botelho Pereira Soares Milena , da Silva Velozo Eudes , Flora Villarreal Cristiane
Published: January 2019

Canthin‐6‐one alkaloids, which are present in plants of the genus Simaba, are natural compounds that are capable of acting as fluorescent probes. However, the chemical composition and fluorescent properties of most species of this genus have not been analyzed. The objective of this study was to characterize the fluorescent properties of an extract of S. bahiensis and identify the chemical entities responsible for these properties. In addition, the cell‐labeling properties of the fluorescent dye from A and of the isolated compounds were characterized by confocal fluorescence microscopy and flow cytometry. One quassinoid and three fluorescent alkaloids were isolated from S. bahiensis, all compounds were identified by using NMR spectroscopy and high‐resolution mass spectrometry. Staining experiments and HPLC‐FL analysis shown that canthin‐6‐one alkaloids are the main green fluorescent compounds in the analyzed dyes. All compounds evaluated showed a cytoplasmic marker with a residence time of 24 h. The present study is the first to describe the presence of canthin‐6‐one alkaloids in S. bahiensis, in addition to demonstrating promising cell‐labeling properties of fluorescent compounds from S. bahiensis with broad emission wavelengths.
Bridging Length Scales by Photochemistry
Authors: Schlüter A. Dieter
Published: January 2019

A. Dieter Schlüter
is a full professor (em.) of polymer chemistry at the Department of Materials at ETH Zürich (Switzerland). He is a current member of the ChemPhotoChem Editorial Board.
Leather‐Promoted Transformation of Glucose into 5‐Hydroxymethylfurfural and Levoglucosenone
Authors: Bobbink Felix D. , Huang Zhangjun , Menoud Florent , Dyson Paul J.
Published: January 2019

The search for efficient catalysts frequently leads to new homogeneous and heterogeneous catalysts of increasing complexity, and sometimes common, natural, or hybrid natural/synthetic materials that could be used in catalysis are overlooked. For example, the leather industry has produced robust Cr‐containing materials for centuries by chemical treatment of animal hides with chromium salts. Herein, the use of chromium‐tanned leather as a heterogeneous catalyst for glucose dehydration to 5‐hydroxymethylfurfural (5‐HMF) and levoglucosenone (LGO) is reported. Four pieces of waste leather were obtained from shoe soles and a belt, characterized by a range of techniques including FTIR spectroscopy, SEM, BET surface area measurements, XRD, and X‐ray photoelectron spectroscopy, and their catalytic activity was evaluated. The activity of the scrap leather pieces compares favorably to those of many recently reported catalysts for the preparation of 5‐HMF, but additionally results in significant quantities of LGO. Overall, the results demonstrate that waste leather is an outstanding material for use in catalysis.
Assembly of Ultra‐Thin NiO Layer Over Zn1−xCdxS for Stable Visible‐Light Photocatalytic Overall Water Splitting
Authors: Ning Xiaofeng , Zhen Wenlong , Zhang Xuqiang , Lu Gongxuan
Published: January 2019

Photocatalytic splitting of water into hydrogen and oxygen by using visible light is considered to be a clean, green, and renewable route for solar energy conversion and storage. Although the Zn1−xCdxS catalysts show comparatively higher activity for photocatalytic hydrogen generation under visible‐light irradiation, they suffer from serious photocorrosion during the photocatalytic reaction. The deposition of a protective layer over the Zn1−xCdxS catalysts is believed to be an effective way to inhibit photocorrosion. However, only a few materials exhibit satisfactory catalytic properties for hydrogen evolution as well as a good protection ability. In this work, a new Zn1−xCdxS photocatalyst was developed for water splitting under visible‐light illumination by assembling an ultrathin NiO layer over Zn0.8Cd0.2S through an in situ photodeposition method. The as‐prepared NiO/Zn0.8Cd0.2S showed significantly higher activity for overall water splitting compared with Pt/Zn0.8Cd0.2S under the same conditions without photocorrosion. An apparent quantum efficiency of 0.66 % was achieved for hydrogen evolution at 430 nm with an accomplished multicycle stability for up to 12 h without any significant decay. The strong electronic coupling between the NiO layer and Zn1−xCdxS also promoted efficient charge separation and migration.