bluuebunny/crossref_metadata_2025_split huggingface dataset:
Survival prognostic factors for metachronous second primary head and neck squamous cell carcinoma
Authors: Chen Jin‐Hua , Yen Yu‐Chun , Chen Tsung‐Ming , Yuan Kevin Sheng‐Po , Lee Fei‐Peng , Lin Kuan‐Chou , Lai Ming‐Tang , Wu Chia‐Che , Chang Chia‐Lun , Wu Szu‐Yuan 
Published: December 2016

AbstractWe examined the overall survival rates of a national cohort to determine optimal treatments and prognostic factors for patients with metachronous second primary head and neck squamous cell carcinomas (mspHNSCCs) at different stages and sites. We analyzed data of mspHNSCC patients collected from the Taiwan Cancer Registry database. The patients were categorized into four groups based on the treatment modality: Group 1 (control arm; chemotherapy [CT] alone), Group 2 (reirradiation [re‐RT] alone with intensity‐modulated radiotherapy [IMRT]), Group 3 (concurrent chemoradiotherapy alone [irradiation with IMRT]), and Group 4 (salvage surgery with or without RT or CT). We enrolled 1741 mspHNSCC patients without distant metastasis. Multivariate Cox regression analyses revealed that Charlson comorbidity index (CCI) ≥6, stage of second HNSCC, stage of first HNSCC, and duration from first primary HNSCC of <3 years were significant poor independent prognostic risk factors for overall survival. After adjustment, adjusted hazard ratios and 95% confidence intervals for the overall all‐cause mortality risk at mspHNSCC clinical stages III and IV were 0.72 (0.40–1.82), 0.52 (0.35–0.75), and 0.32 (0.22–0.45) in Groups 2, 3, and 4, respectively. A Cox regression analysis indicated that a re‐RT dose of ≥6000 cGy was an independent protective prognostic factor for treatment modalities. CCI ≥ 6, stage of second HNSCC, stage of first HNSCC, and duration from first primary HNSCC of <3 years were significant poor independent prognostic risk factors for overall survival. A re‐RT dose of ≥6000 cGy may be necessary for mspHNSCCs.
Coupled Immobilized Amine Dehydrogenase and Glucose Dehydrogenase for Asymmetric Synthesis of Amines by Reductive Amination with Cofactor Recycling
Authors: Liu Ji , Pang Bryan Q. W. , Adams Joseph P. , Snajdrova Radka , Li Zhi 
Published: December 2016

AbstractThe amine dehydrogenase (AmDH) engineered from the phenylalanine dehydrogenase of Rhodococcus sp. M4 was directly immobilized on magnetic nanoparticles (MNP) from the cell‐free extract containing his‐tagged AmDH through affinity attachment to give AmDH‐MNPs with high yield, enzyme loading efficiency, and specific enzyme loading. AmDH‐MNPs showed higher activity and productivity than the free enzyme for the asymmetric reductive amination of 4‐phenyl‐2‐butanone 1 a and phenylacetone 1 b, producing the corresponding amines (R)‐2 a,b in 99 % ee and 99 % yield, and with recycling of NADH for up to 3956 times. AmDH‐MNPs were easily recycled, retaining 91 % of the original productivity in the third cycle of the reductive amination of 1 a. Coupling of immobilized AmDH and immobilized glucose dehydrogenase (GDH) for the asymmetric reductive amination of 1 a gave (R)‐2 a in 99 % ee and 74 % yield, with a total turnover number (TTN) of 2940 for NADH recycling. Both immobilized enzymes showed good recyclability, retaining 81 % productivity in the third reaction cycle. The developed method with coupled immobilized AmDH and immobilized GDH for the asymmetric reductive amination of ketones is useful for the synthesis of enantiopure amines, superior to the use of coupled isolated enzymes with enhanced catalytic performance and reduced enzyme cost through catalyst recycling.
Visible‐Light‐Driven Aerobic Photooxidation of Aldehydes to Methyl Esters Catalyzed by Riboflavin Tetraacetate
Authors: Mühldorf Bernd , Wolf Robert 
Published: December 2016

AbstractRiboflavin tetraacetate (RFT) catalyzes the aerobic esterification of para‐substituted benzaldehydes to their corresponding methyl esters. The reaction proceeds under visible‐light irradiation in MeOH/MeCN in the presence of a Brønsted acid such as HCl. Electron transfer from the in situ formed dimethyl acetal to the photoexcited triplet flavin appears to be a key mechanistic step. The acid catalyzes the formation of the acetal and increases the reduction potential of RFT by protonation. The photocatalyst is regenerated by reaction with atmospheric oxygen, which serves as the terminal oxidant.
Heavy Grignard Reagents: Synthesis, Physical and Structural Properties, Chemical Behavior, and Reactivity
Authors: Westerhausen Matthias , Koch Alexander , Görls Helmar , Krieck Sven 
Published: December 2016

AbstractThe Grignard reaction offers a straight forward atom‐economic synthesis of organomagnesium halides, which undergo redistribution reactions (Schlenk equilibrium) yielding diorganylmagnesium and magnesium dihalides. The homologous organocalcium complexes (heavy Grignard reagents) gained interest only quite recently owing to several reasons. The discrepancy between the inertness of this heavy alkaline earth metal and the enormous reactivity of its organometallics hampered a vast and timely development after the first investigation more than 100 years ago. In this overview the synthesis of organocalcium reagents is described as is the durability in ethereal solvents. Aryl‐, alkenyl‐, and alkylcalcium halides are prepared by direct synthesis. Characteristic structural features and NMR parameters are discussed. Ligand redistribution reactions can be performed by addition of potassium tert‐butanolate to ethereal solutions of arylcalcium iodides yielding soluble diarylcalcium, whereas sparingly soluble potassium iodide and calcium bis(tert‐butanolate) precipitate. Furthermore, reactivity studies with respect to metalation and addition to unsaturated organic compounds and metal‐based Lewis acids, leading to the formation of heterobimetallic complexes, are presented.
Unravelling the Pathway Complexity in Conformationally Flexible N‐Centered Triarylamine Trisamides
Authors: Adelizzi Beatrice , Filot Ivo A. W. , Palmans Anja R. A. , Meijer E. W. 
Published: December 2016

AbstractTwo families of C3‐symmetrical triarylamine‐trisamides comprising a triphenylamine‐ or a tri(pyrid‐2‐yl)amine core are presented. Both families self‐assemble in apolar solvents via cooperative hydrogen‐bonding interactions into helical supramolecular polymers as evidenced by a combination of spectroscopic measurements, and corroborated by DFT calculations. The introduction of a stereocenter in the side chains biases the helical sense of the supramolecular polymers formed. Compared to other C3‐symmetrical compounds, a much richer self‐assembly landscape is observed. Temperature‐dependent spectroscopy measurements highlight the presence of two self‐assembled states of opposite handedness. One state is formed at high temperature from a molecularly dissolved solution via a nucleation–elongation mechanism. The second state is formed below room temperature through a sharp transition from the first assembled state. The change in helicity is proposed to be related to a conformational switch of the triarylamine core due to an equilibrium between a 3:0 and a 2:1 conformation. Thus, within a limited temperature window, a small conformational twist results in an assembled state of opposite helicity.
Structural Transformation from Dimerization to Tetramerization of Serine‐Decorated Rare‐Earth‐Incorporated Arsenotungstates Induced by the Usage of Rare‐Earth Salts
Authors: Li Hai‐Lou , Liu Ya‐Jie , Liu Jing‐Lin , Chen Li‐Juan , Zhao Jun‐Wei , Yang Guo‐Yu 
Published: December 2016

AbstractThree types of serine‐decorated rare‐ earth‐containing arsenotungstate [H2N(CH3)2]6NaH[RE2 W4O10(H2O)8(Ser)2(B‐α‐AsW9O33)2]⋅30 H2O (RE3+=Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, and Y3+; 1), [H2N(CH3)2]6Na6−xRExH4−2 x[RE4W8O19(H2O)10+y(OH)2(Ser)2(B‐α‐AsW9O33)4]⋅n H2O (RE3+=Tb3+, x=1, y=2, n=36; RE3+=Dy3+, Ho3+, Er3+, Yb3+, Y3+, x=0, y=0, n=38; RE3+= Tm3+, x=1, y=0, n=38; Ser=serine; 2), and [H2N(CH3)2]6−2 xNa2+3 xRExH10−6 x+y[RE4W8O19(H2O)8(OH)2(Ser)4(B‐α‐AsW9O33)4]⋅Cly⋅n H2O (RE3+=Ce3+, Pr3+, x=1, y=0, n=65; RE3+=Nd3+, Sm3+, x=0, y=0, n=65; RE3+=Eu3+, Gd3+, x=1, y=2, n=45; 3) were synthesized with the participation of the organic solubilizers dimethylamine hydrochloride and l‐serine and were structurally characterized. The use of different amounts of rare‐earth salts results in the structural transformation from dimerization to tetramerization of types 1–3. Type 1 is a dimeric sandwich‐type assembly of a dual‐Ser‐participating [RE2W4O10(H2O)8(Ser)2]10+ entity sandwiched by two [B‐α‐AsW9O33]9− moieties, whereas types 2 and 3 have a tetrameric square structure formed by four [B‐α‐AsW9O33]9− moieties that anchor a dual/tetra‐ Ser‐participating [RE4W8O19(H2O)10+y(OH)2(Ser)2]20+ or [RE4W8O19(H2O)8(OH)2(Ser)4]20+ core. The solid‐state luminescence properties and lifetime–decay behaviors of these compounds were investigated. The chromaticity coordinates, dominant wavelengths, color purities, and correlated color temperatures were also calculated.
Oxidized Ores as Future Resource for Platinum Group Metals: Current State of Research
Authors: Kraemer Dennis , Junge Malte , Bau Michael 
Published: December 2016

AbstractThe platinum group elements (PGE), which are used in many high technology applications, are classified as critical metals by the EU. Therefore, research has to focus on potential alternative resources. Oxidized ores are found in the weathered zones of common sulfidic deposits, such as the Bushveld and the Great Dyke, and could be considered as potential future resources. The grades and reserves are high. However, due to geochemical and mineralogical changes induced by weathering, extraction of PGE is still limited and uneconomic. The current state of research on oxidized PGE ores in geosciences and processing is summarized.
Neoadjuvant long‐course chemoradiation remains strongly favored over short‐course radiotherapy by radiation oncologists in the United States
Authors: Mowery Yvonne M. , Salama Joseph K. , Zafar S. Yousuf , Moore Harvey G. , Willett Christopher G. , Czito Brian G. , Hopkins M. Benjamin , Palta Manisha 
Published: December 2016

BACKGROUNDShort‐course radiotherapy (SC‐RT) and long‐course chemoradiotherapy (LC‐CRT) are accepted neoadjuvant treatments of rectal cancer. In the current study, the authors surveyed US radiation oncologists to assess practice patterns and attitudes regarding SC‐RT and LC‐CRT for patients with rectal cancer.METHODSThe authors distributed a survey to 1701 radiation oncologists regarding treatment of neoadjuvant rectal cancer. Respondents were asked questions regarding the number of patients with rectal cancer treated, preference for SC‐RT versus LC‐CRT, and factors influencing regimen choice.RESULTSOf 1659 contactable physicians, 182 responses (11%) were received. Approximately 83% treated at least 5 patients with rectal cancer annually. The majority of responding radiation oncologists (96%) preferred neoadjuvant LC‐CRT for the treatment of patients with locally advanced rectal cancer and 44% never used SC‐RT. Among radiation oncologists using SC‐RT, respondents indicated they would not recommend this regimen for patients with low (74%) or bulky tumors (70%) and/or concern for a positive circumferential surgical resection margin (69%). The most frequent reasons for not offering SC‐RT were insufficient downstaging for sphincter preservation (53%) and a desire for longer follow‐up (45%). Many radiation oncologists indicated they would prescribe SC‐RT for patients not receiving chemotherapy (62%) or patients with a geographic barrier to receiving LC‐CRT (82%). Patient comorbidities appeared to influence regimen preferences for 79% of respondents. Approximately 20% of respondents indicated that altered oncology care reimbursement using capitated payment by diagnosis would impact their consideration of SC‐RT.CONCLUSIONSUS radiation oncologists rarely use neoadjuvant SC‐RT despite 3 randomized controlled trials demonstrating no significant differences in outcome compared with LC‐CRT. Further research is necessary to determine whether longer follow‐up coupled with the benefits of lower cost, increased patient convenience, and lower acute toxicity will increase the adoption of SC‐RT by radiation oncologists in the United States. Cancer 2017;123:1434–1441. © 2016 American Cancer Society.
Local therapy reduces the risk of liver failure and improves survival in patients with intrahepatic cholangiocarcinoma: A comprehensive analysis of 362 consecutive patients
Authors: Yamashita Suguru , Koay Eugene Jon , Passot Guillaume , Shroff Rachna , Raghav Kanwal P. , Conrad Claudius , Chun Yun Shin , Aloia Thomas A. , Tao Randa , Kaseb Ahmed , Javle Milind , Crane Christopher H. , Vauthey Jean‐Nicolas 
Published: December 2016

BACKGROUNDTreatment methods for intrahepatic cholangiocarcinoma (ICC) have improved, but their impact on outcome remains unclear. We evaluated the outcomes of patients definitively treated with resection, radiation, and chemotherapy for ICC, stratified by era.METHODSClinico‐pathologic characteristics, cause of death, disease‐specific survival (DSS), and intrahepatic progression‐free survival (IPFS) were compared among patients who underwent resection, radiation, or chemotherapy as definitive treatment strategies for ICC (without distant organ metastasis) between 1997 and 2015. Variables were also analyzed by era (1997‐2006 [early] or 2007‐2015 [late]) within each group.RESULTSAmong 362 patients in our cohort, 122 underwent resection (early, 38; late, 84), 85 underwent radiation (early, 17; late, 68), and 148 underwent systemic chemotherapy alone (early, 51; late, 97) as definitive treatment strategies, and 7 patients received best supportive care. In the resection group, the 3‐year DSS rate was 58% for the early era and 67% for the late era (P = .036), and the 1‐year IPFS was 50% for the early era and 75% for the late era (P = .048). In the radiation group, the 3‐year DSS was 12% for the early era and 37% for the late era (P = .048), and the 1‐year IPFS was 48% for the early era and 64% for the late era (P = .030). In the chemotherapy group, DSS and IPFS did not differ by era. Patients treated with chemotherapy developed liver failure at the time of death significantly more frequently than patients treated with resection (P < .001) or radiation (P < .001). Multivariable analysis identified local therapy (resection or radiation) as a sole predictor of death without liver failure.CONCLUSIONSurvival outcomes have improved for local therapy‐based definitive treatment strategies for ICC, which may be attributable to maintaining control of intrahepatic disease, thereby reducing the occurrence of death due to liver failure. Cancer 2017;123:1354–1362. © 2016 American Cancer Society.
The toxicity and efficacy of concomitant chemoradiotherapy in patients aged 70 years and older with oropharyngeal carcinoma in the intensity‐modulated radiotherapy era
Authors: Zumsteg Zachary S. , Lok Benjamin H. , Ho Allen S. , Drill Esther , Zhang Zhigang , Riaz Nadeem , Shiao Stephen L. , Ma Jennifer , McBride Sean M. , Tsai C. Jillian , Baxi Shrujal S. , Sherman Eric J. , Lee Nancy Y. 
Published: December 2016

BACKGROUNDDespite controversy surrounding its benefit, the use of concomitant chemoradiotherapy (CCRT) in patients with oropharyngeal squamous cell carcinoma (OPSCC) who are aged > 70 years is increasing. However, to the authors' knowledge, few studies to date have compared the outcomes of different systemic treatments in this population.METHODSRecords from 74 patients aged ≥ 70 years with stage III to stage IVB OPSCC who were undergoing CCRT from 2002 to 2013 at a single institution were reviewed. Patients were stratified according to the systemic therapy received, including cisplatin, carboplatin with either 5‐fluorouracil or paclitaxel (CARB), or cetuximab to compare oncologic outcome and toxicity.RESULTSThe median follow‐up was 36 months. The median age of the patients was 75.3 years (range, 70‐91 years), with significantly older patients receiving cetuximab (P = .03). A total of 28, 20, and 26 patients, respectively, received CCRT with cisplatin, CARB, and cetuximab. RT interruptions of > 1 day were needed in 4% of patients receiving cisplatin, 20% of patients receiving CARB, and 15% of patients receiving cetuximab (P = .19). Unplanned hospitalizations during CCRT occurred in 25%, 55%, and 58%, respectively, of patients receiving cisplatin, CARB, and cetuximab (P = .03). There were 2 treatment‐related deaths, both of which occurred among the patients who were treated with cetuximab. At 5 years, locoregional control was achieved in 100%, 88%, and 60% (P<.001), respectively, and the overall survival rate was 87%, 61%, and 47% (P = .03), respectively, among patients treated with cisplatin, CARB, and cetuximab.CONCLUSIONSToxicity from CCRT remains a challenge for older adults with OPSCC. Herein, the authors found no evidence that this toxicity was mitigated by treatment with cetuximab. Nevertheless, a subset of patients aged ≥70 years appear to tolerate cisplatin‐based treatment with acceptable toxicity and excellent outcomes. Further identification of this patient subgroup is crucial to optimize therapy for older patients with OPSCC. Cancer 2017;123:1345–1353. © 2016 American Cancer Society.
Elucidation of the Physicochemical Properties Ruling the Colloidal Stability of Iron Oxide Nanoparticles under Physiological Conditions
Authors: Aires Antonio , Cabrera David , Alonso‐Pardo Laura C. , Cortajarena Aitziber L. , Teran Francisco J. 
Published: December 2016

AbstractNanotechnology has brought countless novel applications regarding therapeutic, diagnostic, and sensing innovations. In particular, nanoparticle engineering enables the synthesis of nanocrystals with customized physical, chemical, and biological activities, which are generally well validated in vitro. However, when nanoparticles are tested in vivo they often show a disappointing loss of efficacy or increase of toxicity. These phenomena are related to the interaction of the nanoparticle surface with proteins, lipids, and ions present in the blood stream. Herein, we assess the physicochemical properties of an array of iron oxide nanoparticles coated with 15 different biocompatible materials dispersed in physiological aqueous media and human blood plasma. Our findings establish valid criteria for the prediction of the colloidal stability of nanoparticles dispersed in physiological aqueous media and human blood plasma. The criteria are based on the hydrophilicity and the net surface charge of the pristine nanoparticle coating in water dispersion. Hence, the methodology to select the most adequate nanoparticle coating for in vivo studies will be improved.
How Dimerization Through a Spiro Junction Modifies the Nonlinear Optical Properties of a Push–Pull Organic Dye: Insights from Theory and Hyper‐Rayleigh Scattering
Authors: Castet Frédéric , Lerychard Timothée , Pielak Kornelia , Szalóki György , Dalinot Clément , Leriche Philippe , Sanguinet Lionel , Champagne Benoît , Rodriguez Vincent 
Published: December 2016

AbstractThe second‐order nonlinear optical (NLO) properties of a push–pull monomer, as well as of its dimer composed of two monomeric units connected through a non‐conjugated spiro junction, are investigated by means of hyper‐Rayleigh scattering (HRS) and quantum chemical calculations. It is shown that dimerization to form a molecule with an orthogonal geometry enhances the first hyperpolarizability by circa 20 % and induces a decrease of the dipolar character of the HRS response. Theoretical calculations correlate well with experimental measurements and allow an in‐depth rationalization of the impact of the spiro linkage on the NLO properties through a detailed analysis of the relevant electronic excited states.
Interplay between Reaction and Phase Behaviour in Carbon Dioxide Hydrogenation to Methanol
Authors: Reymond Helena , Amado‐Blanco Victor , Lauper Andreas , Rudolf von Rohr Philipp 
Published: December 2016

AbstractCondensation promotes CO2 hydrogenation to CH3OH beyond equilibrium through in situ product separation. Although primordial for catalyst and reactor design, triggering conditions as well as the impact on sub‐equilibrium reaction behaviour remain unclear. Herein we used an in‐house designed micro‐view‐cell to gain chemical and physical insights into reaction and phase behaviour under high‐pressure conditions over a commercial Cu/ZnO/Al2O3 catalyst. Raman microscopy and video monitoring, combined with online gas chromatography analysis, allowed the complete characterisation of the reaction bulk up to 450 bar (1 bar=0.1 MPa) and 350 °C. Dew points of typical effluent streams related to a parametric study suggest that the improving reaction performance and reverting selectivities observed from 230 °C strongly correlate with (i) a regime transition from kinetic to thermodynamic, and (ii) a phase transition from a single supercritical to a biphasic reaction mixture. Our results advance a rationale behind transitioning CH3OH selectivities for an improved understanding of CO2 hydrogenation under high pressure.
Microwave‐Assisted Selective Hydrogenation of Furfural to Furfuryl Alcohol Employing a Green and Noble Metal‐Free Copper Catalyst
Authors: Romano Pedro N. , de Almeida João M. A. R. , Carvalho Yuri , Priecel Peter , Falabella Sousa‐Aguiar Eduardo , Lopez‐Sanchez Jose A. 
Published: December 2016

AbstractGreen, inexpensive, and robust copper‐based heterogeneous catalysts achieve 100 % conversion and 99 % selectivity in the conversion of furfural to furfuryl alcohol when using cyclopentyl‐methyl ether as green solvent and microwave reactors at low H2 pressures and mild temperatures. The utilization of pressurized microwave reactors produces a 3–4 fold increase in conversion and an unexpected enhancement in selectivity as compared to the reaction carried out at the same conditions using conventional autoclave reactors. The enhancement in catalytic rate produced by microwave irradiation is temperature dependent. This work highlights that using microwave irradiation in the catalytic hydrogenation of biomass‐derived compounds is a very strong tool for biomass upgrade that offers immense potential in a large number of transformations where it could be a determining factor for commercial exploitation.
Towards Versatile and Sustainable Hydrogen Production through Electrocatalytic Water Splitting: Electrolyte Engineering
Authors: Shinagawa Tatsuya , Takanabe Kazuhiro 
Published: December 2016

AbstractRecent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. Electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible, and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances under which the water splitting reaction is conducted, the required solution conditions, such as the identity and molarity of ions, may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate the development of efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), affect electrode stability, and/or indirectly impact the performance by influencing the concentration overpotential (mass transport). This review aims to guide fine‐tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions.