bluuebunny/crossref_metadata_2025 huggingface dataset:
ОБРАЗОВАНИЕ СВЯЗЕЙ N-S ПРИ ВЗАИМОДЕЙСТВИИ 2- [2-ОКСО-1-(ТОЗИЛОКСИИМИНО)-2-ФЕНИЛЭТИЛ]ПИРИМИДИН-4(3Д)-ОНА И ЕГО 6-ЗАМЕЩЁННЫХ С ТИОМОЧЕВИНОЙ И РОДАНИДОМ КАЛИЯ, "Журнал органической химии"
Authors: Яволовский А.А. , Иванов Ю.Э. , Грищук Л.В. , Кравцов В.Х. , Фонарь М.С. , Камалов Г.Л.
Published: November 2018

Реакция роданида калия с производными 2-[2-оксо-1-(1-тозилоксиимино)-2-фенилэтил]пиримидин- 4(3Н)-она приводит к образованию новой конденсированной гетероциклической системы с общим атомом азота - замещённого 7Н-[1,2,5]тиадиазоло[2,3-а]пиримидин-7-она.
СИНТЕЗ НОВЫХ АМИДОВ ИЗОКСАЗОЛ- И ИЗОТИАЗОЛ- ЗАМЕЩЕННЫХ КАРБОНОВЫХ КИСЛОТ, СОДЕРЖАЩИХ АРИЛАМИНОПИРИМИДИНОВЫЙ ФРАГМЕНТ, "Журнал органической химии"
Authors: Игнатович Ж.В. , Ермолинская А. Л. , Клецков А.В. , Поткин В.И. , Королева Е.В.
Published: November 2018

Ацилированием замещенных 2-аминоарилпиримидинов 5-фенил(п-толил)изоксазол- и 4,5-дихлоризотиазол-3-карбонилхлоридами получены новые амиды пиримидинового ряда.
АЛКИЛИРОВАНИЕ 2-СУЛЬФАНИЛБЕНЗОКСАЗОЛА a-ИОДКЕТОНАМИ В ОТСУТСТВИЕ ОСНОВНЫХ СРЕД, "Журнал органической химии"
Authors: Шагун Л.Г. , Дорофеев И.А. , Жилицкая Л.В. , Ярош Н.О. , Ларина Л.И.
Published: November 2018

При взаимодействии 2-сульфанилбензоксазола с 1-иодпропан-2-оном, 2-иод-1-фенилэтаноном и 2-иод-1-(тиофен-2-ил)этаноном без растворителя в отсутствие оснований получены бис(бензоксазол-2-ил)дисульфонийпроизводные в одну препаративную стадию. Реакция протекает как домино-процесс и включает алкилирование сульфанильной группы бензоксазола, восстановление иодкетона иодоводородом, окисление 2-сульфанилбензоксазола до дисульфида, алкилирование дисульфидных атомов серы, формирование трииодид-анионов. Выход дисульфонийпроизводных увеличивается в 2 раза в присутствии эквимольного количества иода.
ОДНОРЕАКТОРНЫЙ СИНТЕЗ 3,5-ДИЗАМЕЩЁННЫХ 1,2,4-ОКСАДИАЗОЛОВ С ПРИМЕНЕНИЕМ КАТАЛИТИЧЕСКОЙ СИСТЕМЫ NaOH-ДМСО, "Журнал органической химии"
Authors: Панкратьева В.Е. , Шаронова Т.В. , Тарасенко М.В. , Байков С.В. , Кофанов Е.Р.
Published: November 2018

Разработан удобный однореакторный способ получения 3,5-дизамещённых 1,2,4-оксадиазолов при взаимодействии амидоксимов с ангидридами или хлорангидридами карбоновых кислот в системе NaOH-ДМСО. Реакция протекает при комнатной температуре с высокими выходами.
СИНТЕЗ 4-МЕТИЛ-2,6-ДИ(9Н-ТИОКСАНТЕН-9-ИЛ)АНИЛИНА, "Журнал органической химии"
Authors: Горохов В.Ю. , Горохова С.М. , Лысцова Е.А.
Published: November 2018

Синтезирован 4-метил-2,6-ди(9Н-тиоксантен-9-ил)анилин взаимодействием 4-метиланилина с перхлоратом N-тиоксантенилпиридиния в соотношении 1:3 при кратковременном нагревании.
РЕГИОСЕЛЕКТИВНАЯ РЕАКЦИЯ ПИРИДИН-2-СУЛЬФЕНИЛХЛОРИДА С ИЗОЭВГЕНОЛОМ, "Журнал органической химии"
Authors: Ишигеев Р.С. , Потапов В.А. , Амосова С.В.
Published: November 2018

На основе 2,2'-дисульфандиилдипиридина и изоэвгенола разработан региоселективный однореакторный метод синтеза 3-(4-гидрокси-3-метоксифенил)-2-метил-2Н,3Н-[1,3]тиазоло[3,2-а]пиридин-4-ий хлорида с выходом 70%
СИНТЕЗ 4-АМИНО-1,2,4-ТРИАЗИНОВ ИЗ ЭФИРОВ АРОИЛПИРОВИНОГРАДНЫХ КИСЛОТ И ТИОКАРБОГИДРАЗИДА, "Журнал органической химии"
Authors: Кобелев А.И. , Степанова Е.Е. , Масливец А.Н.
Published: November 2018

Эфиры ароилпировиноградных кислот региоселективно взаимодействуют с тиокарбогидразидом с образованием замещенных 4-амино-1,2,4-триазинов.
ВЗАИМОСВЯЗЬ ПЕРВИЧНЫХ ГИДРООПТИЧЕСКИХ ХАРАКТЕРИСТИК НА 650 НМ С ГЛУБИНОЙ ВИДИМОСТИ ДИСКА СЕККИ И КОНЦЕНТРАЦИЕЙ СИНЕ-ЗЕЛЕНЫХ ВОДОРОСЛЕЙ В ГОРЬКОВСКОМ ВОДОХРАНИЛИЩЕ, "Фундаментальная и прикладная гидрофизика"
Authors: Мольков А.А. , Капустин И.А. , Щегольков Ю. Б. , Воденеева Е.Л. , Калашников И. Н.
Published: November 2018

Настоящая работа направлена на исследование гидрооптического режима озерной части Горьковского водохранилища, основанного на судовых и лабораторных измерениях характеристик оптически активных компонентов воды и первичных гидрооптических характеристик, выполненных в 2016 г. Проанализирован массив данных, собранных в период с 27 апреля по 24 октября с 97 станций, покрывающих более половины площади озерной части водохранилища (на участке от дамбы до с. Сокольское). Обнаружено доминирующие влияние сине-зеленых водорослей на прозрачность водной толщи при квазиоднородном пространственно-временном распределении растворенного органического вещества на уровне 11-12 мг/л и пренебрежимо малой концентрации минеральной взвеси. Установлен диапазон изменчивости глубины видимости диска Секки от 0.2 м до 3.5 м при вариации численности сине-зеленых водорослей от 500 до 100 000 клеток/мл соответственно. Для этого диапазона изменчивости найдены регрессии между некоторыми первичными гидрооптическими характеристиками (показателем ослабления и поглощения на длине волны 650 нм) и численностью сине-зеленых водорослей, а также получены простые формулы оценки показателя ослабления и альбедо однократного рассеяния по измерениям глубины видимости диска Секки.
АЛГОРИТМЫ ОПРЕДЕЛЕНИЯ СПЕКТРАЛЬНО-ЭНЕРГЕТИЧЕСКИХ ХАРАКТЕРИСТИК СЛУЧАЙНОГО ПОЛЯ ВНУТРЕННИХ ВОЛН ПО ЛИДАРНЫМ ЭХО-СИГНАЛАМ, "Фундаментальная и прикладная гидрофизика"
Authors: Долина И.С. , Долин Л.С.
Published: November 2018

Теоретически исследована возможность измерения частотно-угловых спектров модовых составляющих случайного поля пикноклинных внутренних волн малой амплитуды лидарным методом. Предложены алгоритмы восстановления спектров внутренних волн по измеренным спектрам относительных флуктуаций мощности лидарного эхо-сигнала с использованием данных о профилях частоты Вяйсяля и первичных гидрооптических характеристик. Показано, что при определенных условиях частотно-угловой спектр флуктуаций мощности эхо-сигнала, приходящего с заданной глубины, представляется в виде суперпозиции частотно-угловых спектров модовых составляющих поля внутренних волн с весовыми множителями, зависящими от профилей первичных гидрооптических характеристик и вертикальной структуры мод. Поэтому спектр одномодового поля внутренних волн может быть определен по флуктуациям эхо-сигнала с одной правильно выбранной глубины, а спектр многомодового поля - по сигналам с нескольких различных глубин, число которых не должно быть меньше числа мод. Приведены формулы для оценки погрешностей определения спектра внутренних волн, обусловленных погрешностью измерения спектра флуктуаций эхо-сигнала, а также погрешностями задания невозмущенного профиля показателя ослабления света и функции, характеризующей вертикальную структуру моды. Процедура восстановления спектров двухмодового поля проиллюстрирована численным экспериментом с использованием реальных гидрологических и гидрооптических данных, полученных в одном из районов Баренцева моря.
ВАЛИДАЦИЯ ДИСТАНЦИОННЫХ ОЦЕНОК ПАРАМЕТРОВ КОККОЛИТОФОРИДНЫХ ЦВЕТЕНИЙ В БАРЕНЦЕВОМ МОРЕ ПО ДАННЫМ НАТУРНЫХ ИЗМЕРЕНИЙ, "Фундаментальная и прикладная гидрофизика"
Authors: Каралли П. Г. , Копелевич О.В. , Салинг И. В. , Шеберстов С.В. , Паутова Л.А. , Силкин В.А.
Published: November 2018

Представлены результаты валидации параметров кокколитофоридных цветений, рассчитанных по данным спутниковых наблюдений и натурных измерений спектрального коэффициента яркости моря R в экспедициях ИО РАН в Баренцевом море в 2016 и 2017 гг. Основные рассматриваемые параметры - концентрация клеток кокколитофорид N, рассчитанная по региональному алгоритму ИО РАН, и концентрация взвешенного неорганического углерода PIC, стандартный продукт НАСА. Оба параметра рассчитываются через показатель рассеяния назад взвешенными частицами b. Выполненная валидация включала, во-первых, оценку ошибок атмосферной коррекции путем сопоставления значений R, рассчитанных по спутниковым данным и данным судового спектрорадиометра. Во-вторых, - валидацию «дистанционных» значений показателя b и концентрации N, используя данные прямых определений концентраций клеток кокколитофорид и отделившихся кокколитов на отобранных пробах морской воды. В-третьих, сопоставление рассчитанных значений N и PIC. Результаты работы показывают, что при благоприятных погодных условиях по спутниковым данным можно получать приемлемые оценки концентрации N; для улучшения точности необходимо учитывать особенности изменчивости характеристик фитопланктона. Получено уравнение регрессии для связи между среднемесячными значениями N и PIC для июля-августа с коэффициентом детерминации 0.82 и относительной ошибкой 18 % для расчета PIC через N.
2018 American College of Rheumatology/National Psoriasis Foundation Guideline for the Treatment of Psoriatic Arthritis
Authors: Singh Jasvinder A. , Guyatt Gordon , Ogdie Alexis , Gladman Dafna D. , Deal Chad , Deodhar Atul , Dubreuil Maureen , Dunham Jonathan , Husni M. Elaine , Kenny Sarah , Kwan‐Morley Jennifer , Lin Janice , Marchetta Paula , Mease Philip J. , Merola Joseph F. , Miner Julie , Ritchlin Christopher T. , Siaton Bernadette , Smith Benjamin J. , Van Voorhees Abby S. , Jonsson Anna Helena , Shah Amit Aakash , Sullivan Nancy , Turgunbaev Marat , Coates Laura C. , Gottlieb Alice , Magrey Marina , Nowell W. Benjamin , Orbai Ana‐Maria , Reddy Soumya M. , Scher Jose U. , Siegel Evan , Siegel Michael , Walsh Jessica A. , Turner Amy S. , Reston James
Published: November 2018

Objective

To develop an evidence‐based guideline for the pharmacologic and nonpharmacologic treatment of psoriatic arthritis (PsA), as a collaboration between the American College of Rheumatology (ACR) and the National Psoriasis Foundation (NPF).

Methods

We identified critical outcomes in PsA and clinically relevant PICO (population/intervention/comparator/outcomes) questions. A Literature Review Team performed a systematic literature review to summarize evidence supporting the benefits and harms of available pharmacologic and nonpharmacologic therapies for PsA. GRADE (Grading of Recommendations Assessment, Development and Evaluation) methodology was used to rate the quality of the evidence. A voting panel, including rheumatologists, dermatologists, other health professionals, and patients, achieved consensus on the direction and the strength of the recommendations.

Results

The guideline covers the management of active PsA in patients who are treatment‐naive and those who continue to have active PsA despite treatment, and addresses the use of oral small molecules, tumor necrosis factor inhibitors, interleukin‐12/23 inhibitors (IL‐12/23i), IL‐17 inhibitors, CTLA4‐Ig (abatacept), and a JAK inhibitor (tofacitinib). We also developed recommendations for psoriatic spondylitis, predominant enthesitis, and treatment in the presence of concomitant inflammatory bowel disease, diabetes, or serious infections. We formulated recommendations for a treat‐to‐target strategy, vaccinations, and nonpharmacologic therapies. Six percent of the recommendations were strong and 94% conditional, indicating the importance of active discussion between the health care provider and the patient to choose the optimal treatment.

Conclusion

The 2018 ACR/NPF PsA guideline serves as a tool for health care providers and patients in the selection of appropriate therapy in common clinical scenarios. Best treatment decisions consider each individual patient situation. The guideline is not meant to be proscriptive and should not be used to limit treatment options for patients with PsA.
Functionalized Holmium‐Doped Hollow Silica Nanospheres for Combined Sonodynamic and Hypoxia‐Activated Therapy
Authors: Wang Yanke , Liu Yan , Wu Huixia , Zhang Jianping , Tian Qiwei , Yang Shiping
Published: November 2018

The oxygen concentration dependence of sonodynamic therapy (SDT) and bioreductive therapy can be utilized to design the strategy of synergistic therapy. Herein, holmium‐doped hollow silica nanospheres are synthesized and then sequentially modified with chlorin e6, carboxyl poly(ethylene glycol) silane, and prostate stem cell antigen (PSCA) monoclonal antibody. The resultant nanocomposite designated as HHSN‐C/P‐mAb has good biocompatibility and can specifically target cancer cells overexpressing PSCA. Due to the inner cavity structure and Ho doping, HHSN‐C/P‐mAb shows high ultrasound (US) imaging contrast capability and excellent high‐field magnetic resonance contrast performance. HHSN‐C/P‐mAb can act as a nanocarrier for loading the bioreductive pro‐drug tirapazamine (TPZ), and the degradation of the hollow nanospheres under the trigger of acidic microenvironment favors the pH responsive release of TPZ from the material. Upon US irradiation, HHSN‐C/P‐mAb produces reactive oxygen species to kill the cancer cells, and importantly, the oxygen consumption during SDT induces an intratumoral hypoxic environment to activate the therapeutic function of codelivered TPZ, resulting in a high‐effective synergistic therapy. The findings of this study highlight that HHSN‐C/P‐mAb is a versatile theranostic nanoplatform for efficient cancer treatment.
Cadmium Sulfide Quantum‐Dot‐Photocatalyzed Cascade Cyclization of Functionalized Difluoromethyl Chlorides with Unactivated Olefins
Authors: Hu Jinglin , Pu Tong‐Jun , Xu Zhuo‐Wei , Xu Wen‐Yi , Feng Yi‐Si
Published: November 2018

A cadmium sulfide quantum‐dot‐photocatalyzed C(sp3)−Cl bond cleavage of ethyl chlorodifluoroacetate and cascade cyclization with unactivated olefins is described herein. This reaction provides a cost‐efficient method for synthesizing a wide range of CF2‐containing azaheterocycles from a variety of functionalized difluoromethyl chlorides. Furthermore, the results of a preliminary anti‐proliferative activity study indicate an in vitro anti‐proliferative activity superior to that of doxorubicin with IC50 values of 1.140 μM on triple negative breast cancer (MDA‐MB‐231) and 2.129 μM on lung (A549) carcinoma cells.

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Regiodivergent Control in the Gold(I) Catalyzed Synthesis of 7‐Pyrazolylindoles from 1‐Propargyl‐1H‐benzotriazoles and Ynamides through α‐Imino Gold(I) Carbene Complexes
Authors: Allegue Darío , González Jairo , Fernández Sergio , Santamaría Javier , Ballesteros Alfredo
Published: November 2018

A smooth, gold catalyzed, atom‐economical and regioselective synthesis of indoles is reported here. The reaction occurs from a nucleophilic attack of in situ synthesized triazapentalenes to gold activated ynamides and involves the participation of α‐imino gold carbene complexes. The use of sulfonyl ynamides drives the reaction to the formation of 2‐amidosubstituted indoles. However, the employment of 2‐oxazolidinolylynamides allows the formation of both isomers, such as, 2‐amido‐ and 3‐amidosubstituted indoles. In this case, the regioselection could be controlled by a correct choice of the catalyst ligand and the electron‐donating capability of the aryl substituent of the ynamide. A correct control in both parameters permits a totally regioselective synthesis of one or the other regioisomer. Isolation of key intermediates and X‐ray analysis allowed for a plausible explanation for this behavior.

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2D Nitrogen‐Containing Carbon Material C5N as Potential Host Material for Lithium Polysulfides: A First‐Principles Study
Authors: Wang Dandan , Li Haibo , Zhang Liangliang , Sun Zhonghui , Han DongXue , Niu Li , Zhao Jialong
Published: November 2018

Two‐dimensional (2D) materials are identified to be efficient in many applications. In this work, a novel 2D nitrogen‐containing carbon material, C5N, is theoretically designed through structure changes in atomic scale, that is, introducing VC–VN bivacancy defects along lines in perfect C3N monolayer. C5N monolayer is verified to be chemically, mechanically, dynamically, and thermodynamically stable based on cohesive energy, elastic constants, phonon spectrum, and molecular dynamics calculations. C5N is determined to be metallic which is an important property for battery electrode. Moreover, the anchoring performance of S8 and Li2Sn (n = 1, 2, 4, 6, and 8) on C5N monolayer and the anchoring mechanisms are explored. The adsorption energies are calculated to be −0.24, −1.20, −1.10, −1.06, −1.63, and −1.59 eV for S8, Li2S8, Li2S6, Li2S4, Li2S2, and Li2S, respectively. The anchoring effect of Li2Sn on C5N monolayer originates from the charge transfer between lithium polysulfides and C5N surface. These results reveal that C5N monolayer is a promising host material for polysulfides in Li–S batteries. Our calculations illustrate the design of nanostructures and facilitate the application of carbon‐based 2D materials in environment and energy.
Enhanced Switching Stability in Forming‐Free SiNx Resistive Random Access Memory Devices with Low Power Consumptions Based on Local Pt Doping in a Stacked Structure
Authors: Jiang Peng Fei , Gao Hai Xia , Yang Mei , Zhang Zhen Fei , Ma Xiao Hua , Yang Yin Tang
Published: November 2018

In this study, forming‐free and reliable resistive switching characteristics are demonstrated by using Pt doping in a stacked structure of SiNx resistive random access memory cells. Pt nanoparticles are embedded in situ and the size of them are about 1–2 nm. It ensures the potential of size scaling for the devices. Compared to those without Pt doping, a more reliable switching stability with better endurance and retention characteristics is obtained. The operating voltages and currents are low so that it is suitable for low power consumption applications. Films deposited at higher temperature show better compactness.
Surface State‐Mediated Charge Transfer of Cs2SnI6 and Its Application in Dye‐Sensitized Solar Cells
Authors: Shin HyeonOh , Kim Byung‐Man , Jang Taehyung , Kim Kwang Min , Roh Deok‐Ho , Nam Jung Seung , Kim Jeong Soo , Kim Un‐Young , Lee Byunghong , Pang Yoonsoo , Kwon Tae‐Hyuk
Published: November 2018

A vacancy‐ordered double perovskite, Cs2SnI6, has emerged as a promising lead‐free perovskite in the optoelectronic field. However, the charge transfer kinetics mediated by its surface state remains unclear. Here, the charge transfer mechanism of Cs2SnI6 is reported and the role of its surface state in the presence of a redox mediator is clarified. Specifically, charge transfer through the surface state of Cs2SnI6 and its subsequent surface state charging are demonstrated by cyclic voltammetry and Mott–Schottky measurements, respectively. Because it is expected that the surface state of Cs2SnI6 is capable of regenerating oxidized organic dyes, a Cs2SnI6‐based regenerator is developed for a dye‐sensitized solar cell composed of fluorine‐doped tin oxide (FTO)/dyed mesoporous TiO2/regenerator/poly(3,4‐ethylenedioxythiophene)/FTO. As expected, the performance of the Cs2SnI6‐based regenerator is strongly dependent on the highest occupied molecular orbital of the dyes. Consequently, Cs2SnI6 shows efficient charge transfer with a thermodynamically favorable charge acceptor level, achieving a 79% enhancement in the photocurrent density (14.1 mA cm−2) compared with that of a conventional liquid electrolyte (7.9 mA cm−2). The results suggest that the surface state of Cs2SnI6 is the main charge transfer pathway in the presence of a redox mediator and should be considered in future designs of Cs2SnI6‐based devices.
Factors associated with medication adherence in older patients: A systematic review
Authors: Smaje Ashley , Weston‐Clark Maryse , Raj Ranjana , Orlu Mine , Davis Daniel , Rawle Mark
Published: November 2018

Objective

Medication adherence is a major challenge in the treatment of older patients; however, they are under‐represented in research. We undertook a systematic review focused on older patients to assess the reasons underlying non‐adherence in this population.

Methods

We searched multiple electronic databases for studies reporting reasons for non‐adherence to medication regimens in patients aged 75 years and over. Our results were not limited to specific diseases, health‐care settings, or geographical locations. The quality of eligible studies was assessed using the Newcastle‐Ottawa Scale. A narrative synthesis of findings was performed.

Results

A total of 25 publications were included, all of which were in community settings. Frequent medication review and knowledge regarding the purpose of the medication were positively associated with adherence. Factors associated with poor adherence were multimorbidity, cognitive impairment, complex regimens with multiple prescribing physicians, and problems with drug storage or formulation.

Conclusion

These findings suggest that interventions to improve adherence could focus on medication review aimed at simplifying regimens and educating patients about their treatment. Groups with poor adherence that may benefit most from such a model include patients with multiple comorbidities and cognitive impairment.
Probing Hyperconjugative Aromaticity of Monosubstituted Cyclopentadienes
Authors: Xie Qiong , Sun Tingting , Orozco‐Ic Mesías , Barroso Jorge , Zhao Yu , Merino Gabriel , Zhu Jun
Published: November 2018

Hyperconjugation and aromaticity are two of the most important concepts in chemistry. Mulliken and co‐workers combined both terms to explain the stability of cyclopentadiene. Here, we carried out DFT calculations on a series of mono‐ and disubstituted cyclopentadiene derivatives to investigate their hyperconjugative aromaticity. Our results revealed that one electropositive substituent can induce aromaticity, whereas one electronegative substituent prompts nonaromaticity rather than antiaromaticity. When an electronegative substituent and a transition metal as an electropositive substituent were considered simultaneously, a slightly aromatic cyclopentadiene ring could be achieved, whereas an electropositive substituent of the main group in combination with an electronegative one will produce a nonaromatic cyclopentadiene ring.
Antioxidant Grain Passivation for Air‐Stable Tin‐Based Perovskite Solar Cells
Authors: Tai Qidong , Guo Xuyun , Tang Guanqi , You Peng , Ng Tsz‐Wai , Shen Dong , Cao Jiupeng , Liu Chun‐Ki , Wang Naixiang , Zhu Ye , Lee Chun‐Sing , Yan Feng
Published: November 2018

Tin‐based perovskites with excellent optoelectronic properties and suitable band gaps are promising candidates for the preparation of efficient lead‐free perovskite solar cells (PSCs). However, it is challenging to prepare highly stable and efficient tin‐based PSCs because Sn2+ in perovskites can be easily oxidized to Sn4+ upon air exposure. Here we report the fabrication of air‐stable FASnI3 solar cells by introducing hydroxybenzene sulfonic acid or its salt as an antioxidant additive into the perovskite precursor solution along with excess SnCl2. The interaction between the sulfonate group and the Sn2+ ion enables the in situ encapsulation of the perovskite grains with a SnCl2–additive complex layer, which results in greatly enhanced oxidation stability of the perovskite film. The corresponding PSCs are able to maintain 80 % of the efficiency over 500 h upon air exposure without encapsulation, which is over ten times longer than the best result reported previously. Our results suggest a possible strategy for the future design of efficient and stable tin‐based PSCs.
Late‐Stage Peptide Diversification through Cobalt‐Catalyzed C−H Activation: Sequential Multicatalysis for Stapled Peptides
Authors: Lorion Mélanie M. , Kaplaneris Nikolaos , Son Jongwoo , Kuniyil Rositha , Ackermann Lutz
Published: November 2018

Bioorthogonal late‐stage diversification of structurally complex peptides has enormous potential for drug discovery and molecular imaging. In recent years, transition‐metal‐catalyzed C−H activation has emerged as an increasingly viable tool for peptide modification. Despite major accomplishments, these strategies largely rely on expensive palladium catalysts. We herein report an unprecedented cobalt(III)‐catalyzed peptide C−H activation, which enables the direct C−H functionalization of structurally complex peptides, and sets the stage for a multicatalytic C−H activation/alkene metathesis/hydrogenation strategy for the assembly of novel cyclic peptides.
Optical Chirality Sensing with an Auxiliary‐Free Earth‐Abundant Cobalt Probe
Authors: De los Santos Zeus A. , Lynch Ciarán C. , Wolf Christian
Published: November 2018

Broadly useful chiroptical enantiomeric excess (ee) sensing remains challenging and typically involves carefully designed molecular receptors or supramolecular assemblies. Herein, we report on the enantioselective sensing of 35 amino acids, amino phosphonic acids, hydroxy acids, amino alcohols, and diamines with an auxiliary‐free cobalt probe. Chiroptical analysis of the enantiomeric composition and concentration of minute sample amounts was achieved with high accuracy by using earth‐abundant cobalt salts and hydrogen peroxide as the oxidant. Despite the absence of an auxiliary ligand, the cobalt assay is applicable to aromatic and aliphatic compounds and yields strong CD signals at high wavelengths. This method obviates the general prerequisite for chromophoric metal ligands to generate chiroptical signals through ECCD (exciton‐coupled circular dichroism) effects or through analyte‐to‐ligand chirality induction, and it offers operational simplicity, cost efficiency, waste reduction, and speed.
Exploring the Fundamental Structures of Life: Non‐Targeted, Chemical Analysis of Single Cells and Subcellular Structures
Authors: Neumann Elizabeth K. , Do Thanh D. , Comi Troy J. , Sweedler Jonathan V.
Published: November 2018

Cells are a basic functional and structural unit of living organisms. Both unicellular communities and multicellular species produce an astonishing chemical diversity, enabling a wide range of divergent functions, yet each cell shares numerous aspects that are common to all living organisms. While there are many approaches for studying this chemical diversity, only a few are non‐targeted and capable of analyzing hundreds of different chemicals at cellular resolution. Here, we review the non‐targeted approaches used to perform comprehensive chemical analyses, provide chemical imaging information, or obtain high‐throughput single‐cell profiling data. Single‐cell measurement capabilities are rapidly increasing in terms of throughput, limits of detection, and completeness of the chemical analyses; these improvements enable their application to understand ever more complex physiological phenomena, such as learning, memory, and behavior.
Phase Separation and Transcription Regulation: Are Super‐Enhancers and Locus Control Regions Primary Sites of Transcription Complex Assembly?
Authors: Gurumurthy Aishwarya , Shen Yong , Gunn Eliot M. , Bungert Jörg
Published: November 2018

It is proposed that the multiple enhancer elements associated with locus control regions and super‐enhancers recruit RNA polymerase II and efficiently assemble elongation competent transcription complexes that are transferred to target genes by transcription termination and transient looping mechanisms. It is well established that transcription complexes are recruited not only to promoters but also to enhancers, where they generate enhancer RNAs. Transcription at enhancers is unstable and frequently aborted. Furthermore, the Integrator and WD‐domain containing protein 82 mediate transcription termination at enhancers. Abortion and termination of transcription at the multiple enhancers of locus control regions and super‐enhancers provide a large pool of elongation competent transcription complexes. These are efficiently captured by strong basal promoter elements at target genes during transient looping interactions.
Early metabolic characterization of brain tissues after whole body radiation based on gas chromatography–mass spectrometry in a rat model
Authors: Yao Xueting , Xu Chao , Cao Yurong , Lin Lin , Wu Hanxu , Wang Chang
Published: November 2018

Radiation‐induced brain injury involves acute, early delayed and late delayed damage based on the time‐course and clinical manifestations. The acute symptoms are mostly transient and reversible, whereas the late delayed radiation‐induced changes are progressive and irreversible. Therefore, evaluation of the organ‐specific early response to ionizing radiation exposure is necessary for improving treatment strategies and minimizing possible damage at an early stage after radiation exposure. In the current study, the gas chromatography–mass spectrometry technique based on metabolomics coupled with metabolic correlation network was applied to investigate the early metabolic characterization of rat brain tissues following irradiation. Our findings showed that the metabolic response to irradiation was not just limited to the variations of individual metabolite levels, but also accompanied by alterations of network correlations among various metabolites. Metabolite clustering indicated that energy metabolism disorder and inflammation response were induced following radiation exposure. The correlation networks revealed that the strong positive correlations of differential metabolites were highly reduced and significant negative linkages were highlighted in irradiated groups even without statistical changes in metabolic levels. Our findings provided new insights into our understanding of the radiation‐induced acute brain injury mechanism and clues as to the therapy target for clinical applications.
Development of supervision personalisation forms: A qualitative study of the dimensions along which supervisors’ practices vary
Authors: Wallace Kirsty , Cooper Mick
Published: November 2018

Aim

The purpose of this study was to identify dimensions for a new pair of supervisory tools: the supervision personalisation form (SPF) and the supervision personalisation form – assessment (SPF‐A). These are intended to help tailor supervisory work to the individual supervisee's needs and preferences.

Method

Semi‐structured qualitative interviews were conducted with 15 accredited supervisors (four males and 11 females), principally counsellors and psychotherapists of an integrative or humanistic orientation, to identify the main dimensions along which their supervision practice varied. Data were analysed thematically using principles from grounded theory.

Results

Eleven dimensions of supervisory practice were identified: (1) Offering more, or less, theoretical input; (2) Focusing on the supervisee's strengths vs. focusing on their difficulties; (3) Focusing more, or less, on the supervisory relationship; (4) Providing more, or less, structure; (5) Focusing on the client's issues vs. focusing on the supervisee's issues; (6) Offering more, or less, self‐disclosure; (7) Drawing from one, or more than one, orientation; (8) Offering more, or less, techniques and exercises; (9) Suggesting reading and reflection outside of supervision vs. not doing this; (10) More, or less, talking; (11) Directly challenging the supervisee vs. not directly challenging them.

Discussion

These 11 dimensions have been transposed into items for the SPF and SPF‐A, which are now available for use in supervisory practice. However, further testing, evaluation and refinement of the forms is needed.
Provision of mental health interventions in women's centres: An exploratory study
Authors: Hatchett Victoria , Pybis Jo , Tebbet‐Duffin Ursula , Rowland Nancy
Published: November 2018

Background

Women's centres are community‐based third sector organisations providing gender‐specific services to vulnerable females, including offenders and those at risk of offending. Mental health is a particular need within this population; however, there is limited knowledge of the type(s) and availability of mental health interventions within women's centres.

Aims

To explore the provision of mental health interventions within women's centres, providing an overview of services and the extent to which they evaluate interventions offered.

Method

A 32‐item online survey was developed, and 48 services across England and Wales were invited to participate. Data collected were exported from the survey host website and analysed descriptively.

Results

Thirty‐four services took part in the survey. Over two‐thirds provided psychological interventions, with counselling being the most frequently offered type of therapy. Clients presented to services with a range of issues, including mental health problems, personality disorder and self‐harm. Thirteen services undertook evaluations of interventions; data gathered were used for a variety of purposes, including improving interventions and justifying service provision.

Conclusions

This exploratory study provides information about current mental health provision in women's centres and the range of needs experienced by clients. We need to increase our knowledge and understanding of provision within these services, develop a standardised approach to client data collection and management, and create a robust package of valid and reliable outcome measures for use across services. This will augment routine evaluation of the effectiveness and cost‐effectiveness of these services in meeting the health, well‐being and offending needs of female clients.
Linking self‐determined needs and word of mouth to consumer e‐waste disposal behaviour: A test of basic psychological needs theory
Authors: Gilal Faheem Gul , Zhang Jian , Gilal Naeem Gul , Gilal Rukhsana Gul
Published: November 2018

E‐waste is recognized as the fastest growing waste stream in the world. It contains toxic substances such as heavy metals and flame retardants that are hazardous to human and ecological health. Despite these environmental and health hazards, the vast majority of consumers are reluctant to dispose of e‐waste and prefer to store obsolete products at home instead of returning them to manufacturers for recycling. To address this alarming problem, we use the basic psychological needs theory (BPNT) and word of mouth (WOM) to profile consumer behaviour changes and explain self‐reported consumer e‐waste disposal behaviours. Based on longitudinal survey data collected over two rounds from Pakistan, the findings support the role of BPNT. Particularly, the results show that positive WOM messages about e‐waste disposal significantly improve consumers' self‐determined needs that, in turn, fuel consumers' integrated motivation for e‐waste and subsequent e‐waste disposal behaviours. The implications of these findings for practitioners regarding consumer behavioural changes are discussed in‐depth.
Atherectomy in below‐the‐knee endovascular interventions: One‐year outcomes from the XLPAD registry
Authors: Khalili Houman , Jeon‐Slaughter Haekyung , Armstrong Ehrin J. , Baskar Amutharani , Tejani Ishita , Shammas Nicolas W. , Prasad Anand , Abu‐Fadel Mazen , Brilakis Emmanouil S. , Banerjee Subhash
Published: November 2018

Background

Use of atherectomy for the treatment of peripheral arterial disease (PAD) is increasing as an adjunctive treatment to either conventional or drug‐coated balloon angioplasty. There is limited data on atherectomy outcomes in below‐the‐knee (BTK) endovascular interventions.

Methods

Data from the multicenter Excellence in Peripheral Artery Disease (XLPAD) registry (NCT01904851) were analyzed to examine predictors of atherectomy use and its associated 1‐year patency rate. We analyzed 518 BTK procedures performed between January 2005 and December 2016.

Results

Overall a total of 518 BTK procedures were treated in 430 patients, and 43% of interventions used atherectomy. African American patients were less likely (13% vs 25%; |standard residual| = 3.41) to be treated with atherectomy. Use of atherectomy was lower in chronic total occlusive (CTO) lesions (48% vs 58%; P = 0.02). There were no significant associations of baseline comorbidities, critical limb ischemia (CLI), ankle‐brachial index, number of BTK vessel run‐off, or vessel location with atherectomy use. Compared with patients without atherectomy, use of atherectomy was associated with lower incidence of repeat target limb intervention at 1 year after adjusting for age, CLI, in‐stent restenosis, heavy calcification, presence of diffuse disease, and CTO lesion traits (Hazard Ratio 0.41, 95% confidence interval 0.23‐0.72; P < 0.01).

Conclusions

Compared with no atherectomy, use of atherectomy in BTK interventions is associated with lower rates of 1‐year repeat target limb revascularization. These findings require confirmation in prospective, randomized clinical studies.
Heterogeneous Photocatalyzed C−C Cross‐coupling Reactions Under Visible‐light and Near‐infrared Light Irradiation
Authors: Gu Quan , Jia Qiaohui , Long Jinlin , Gao Ziwei
Published: November 2018

With the development of photocatalytic technology and organic synthesis chemistry, the photocatalyzed cross‐coupling reaction provides one of the most attractive methodologies for the C−C bond formation and has been booming in recent years. The advantages of the heterogeneous photocatalyzed C−C cross‐coupling reaction lie in its environment friendly, easily separated and conveniently recovered catalysts. In this review, we summarized and highlighted recent achievements of heterogeneous photocatalyzed C−C cross‐coupling reactions through four aspects: visible light induced C−C cross‐coupling reactions catalyzed by Pd supported semiconductor photocatalysts; visible light induced C−C cross‐coupling reactions catalyzed by Pd based plasmonic photocatalysts; visible light induced C−C cross‐coupling reactions catalyzed by palladium‐free photocatalysts; near‐infrared light induced C−C cross‐coupling reactions.
Neoadjuvant therapy for esophageal cancer: Who, when, and what?
Authors: Greally Megan , Ilson David H.
Published: November 2018

The perioperative combination of 5‐fluorouracil, oxaliplatin, and docetaxel is a new standard treatment in patients with esophageal carcinoma. However, chemoradiation results in higher R0 surgical resection rates, pathologic complete response, and negative lymph node status. The identification of molecular subsets may influence the design of future studies and guide drug development.
Hispanic ethnicity as a moderator of the effects of aerobic and resistance exercise in survivors of breast cancer
Authors: Dieli‐Conwright Christina M. , Sweeney Frank C. , Courneya Kerry S. , Tripathy Debu , Sami Nathalie , Lee Kyuwan , Buchanan Thomas A. , Spicer Darcy , Bernstein Leslie , Mortimer Joanne E. , Demark‐Wahnefried Wendy
Published: November 2018

Background

Metabolic syndrome (MSY) is associated with an increased risk of cardiovascular disease, type 2 diabetes, and recurrence in breast cancer survivors (BCS). MSY is 1.5 times more common in Hispanic women compared with non‐Hispanic women. Although exercise mitigates MSY in BCS, to the best of the authors’ knowledge, few studies to date have focused on minorities. This secondary analysis examined ethnicity as a moderator of the effects of a 16‐week aerobic and resistance exercise intervention on MSY, sarcopenic obesity, and serum biomarkers in BCS.

Methods

A total of 100 eligible BCS were randomized to exercise (50 BCS) or usual care (50 BCS). The exercise intervention promoted moderate to vigorous aerobic and resistance exercise 3 times a week for 16 weeks. MSY z scores, sarcopenic obesity, and serum biomarkers were measured at baseline, after the intervention, and at the 28‐week follow‐up (exercise group only). Linear mixed models adjusted for baseline values of the outcome, age, disease stage, adjuvant treatment, and recent physical activity were used to evaluate effect modification by ethnicity.

Results

The study sample was 57% Hispanic BCS (HBCS) and 43% non‐Hispanic BCS (NHBCS). HBCS were younger, of greater adiposity, and had been diagnosed with more advanced cancers compared with NHBCS (P<.001). Ethnicity was found to moderate the mean differences in exercise training on triglycerides (‐36.4 mg/dL; 95% confidence interval [95% CI],‐64.1 to ‐18.8 mg/dL), glucose (‐8.6 mg/dL; 95% CI, ‐19.1 to ‐3.0 mg/dL), and C‐reactive protein (‐3.3 mg/L; 95% CI, ‐7.3 to ‐0.9 mg/L).

Conclusions

HBCS appear to have poorer metabolic profiles and therefore may derive relatively larger metabolic changes from exercise compared with NHBCS. Clinical exercise interventions may attenuate existing health disparities across diverse groups of BCS.
The distribution of T‐cell subsets and the expression of immune checkpoint receptors and ligands in patients with newly diagnosed and relapsed acute myeloid leukemia
Authors: Williams Patrick , Basu Sreyashi , Garcia‐Manero Guillermo , Hourigan Christopher S. , Oetjen Karolyn A. , Cortes Jorge E. , Ravandi Farhad , Jabbour Elias J. , Al‐Hamal Zainab , Konopleva Marina , Ning Jing , Xiao Lianchun , Hidalgo Lopez Juliana , Kornblau Steve M. , Andreeff Michael , Flores Wilmer , Bueso‐Ramos Carlos , Blando Jorge , Galera Pallavi , Calvo Katherine R. , Al‐Atrash Gheath , Allison James P. , Kantarjian Hagop M. , Sharma Padmanee , Daver Naval G.
Published: November 2018

Background

Phenotypic characterization of immune cells in the bone marrow (BM) of patients with acute myeloid leukemia (AML) is lacking.

Methods

T‐cell infiltration was quantified on BM biopsies from 13 patients with AML, and flow cytometry was performed on BM aspirates (BMAs) from 107 patients with AML who received treatment at The University of Texas MD Anderson Cancer Center. The authors evaluated the expression of inhibitory receptors (programmed cell death protein 1 [PD1], cytotoxic T‐lymphocyte antigen 4 [CTLA4], lymphocyte‐activation gene 3 [LAG3], T‐cell immunoglobulin and mucin‐domain containing‐3 [TIM3]) and stimulatory receptors (glucocorticoid‐induced tumor necrosis factor receptor‐related protein [GITR], OX40, 41BB [a type 2 transmembrane glycoprotein receptor], inducible T‐cell costimulatory [ICOS]) on T‐cell subsets and the expression of their ligands (41BBL, B7‐1, B7‐2, ICOSL, PD‐L1, PD‐L2, and OX40L) on AML blasts. Expression of these markers was correlated with patient age, karyotype, baseline next‐generation sequencing for 28 myeloid‐associated genes (including P53), and DNA methylation proteins (DNA methyltransferase 3α, isocitrate dehydrogenase 1[IDH1], IDH2, Tet methylcytosine dioxygenase 2 [TET2], and Fms‐related tyrosine kinase 3 [FLT3]).

Results

On histochemistry evaluation, the T‐cell population in BM appeared to be preserved in patients who had AML compared with healthy donors. The proportion of T‐regulatory cells (Tregs) in BMAs was higher in patients with AML than in healthy donors. PD1‐positive/OX40‐positive T cells were more frequent in AML BMAs, and a higher frequency of PD1‐positive/cluster of differentiation 8 (CD8)‐positive T cells coexpressed TIM3 or LAG3. PD1‐positive/CD8‐positive T cells were more frequent in BMAs from patients who had multiply relapsed AML than in BMAs from those who had first relapsed or newly diagnosed AML. Blasts in BMAs from patients who had TP53‐mutated AML were more frequently positive for PD‐L1.

Conclusions

The preserved T‐cell population, the increased frequency of regulatory T cells, and the expression of targetable immune receptors in AML BMAs suggest a role for T‐cell–harnessing therapies in AML.
Optimization of high performance m‐aramid fiber with disperse dye containing high color strength
Authors: Azam Farooq , Iqbal Kashif , Safdar Faiza
Published: November 2018

This study focuses on the optimization of parameters involved in the process of dyeing such as temperature, concentration of dye, and swelling agent for m‐aramid fibers with disperse dyes and these parameters were used to investigate the shade depth and fastness properties of m‐aramid fibers. Experiments were carried out in batch system to study the effect of factors and their levels mainly on shade depth of the fibers. The shade depth, that is, K/S value of m‐aramid fibers was improved proportionally with the increasing concentration of swelling agent and dye concentration.
The personal authentication service and security enhancement for optimal strong password
Authors: ShanmugaPriya S. , Valarmathi A. , Yuvaraj D.
Published: November 2018

The ability of the Cloud to share information and provide certain services to the network linked people. The resources are provided according to the need of the user. In cloud, the user's data are moved to the large data storage, which must be secured. The various organization have expressed concerns about security aspects of cloud computing. One of the major perspectives is to provide security to one's data, which is stored remotely from the user's location. This paper describes an enhanced approach for the already used data security model in cloud environment. The proposed data security model includes generation of OTP using HMAC (Hash based message authentication code) for user authentication process. This paper also includes a comparative MD5 and SHA algorithms for the better implementation of the model. This model best suits for any of the layers in it, to achieve this we use certain encryption algorithms that convert original text to the form that is not understood by the third party. Finally, data availability can be considered as a major concern, which is viewed as threat associated with the cloud environment. To overcome this problem, we generally replicate our data and store it in various locations.
Comparative Effectiveness and Safety of Standard or Reduced Dose Dabigatran vs. Rivaroxaban in Nonvalvular Atrial Fibrillation
Authors: Blin Patrick , Dureau‐Pournin Caroline , Cottin Yves , Bénichou Jacques , Mismetti Patrick , Abouelfath Abdelilah , Lassalle Regis , Droz Cécile , Moore Nicholas
Published: November 2018

Dabigatran and rivaroxaban at standard or reduced doses have been compared to warfarin in nonvalvular atrial fibrillation (NVAF), but not to each other. This was a new user study of standard dose and reduced dose dabigatran or rivaroxaban for NVAF in the French healthcare database, matched on gender, age, date of first dispensing, and high‐dimensional propensity score, followed 2 years. Hazard ratios (HRs; 95% confidence intervals (CI)) of stroke or systemic embolism (SSE), major bleeding (MB), or death were computed. In matched standard‐dose patients (8,290 per arm), mean age 67 years, HRs for dabigatran vs. rivaroxaban were SSE 0.92 (95% CI = 0.67–1.26), MB 0.59 (95% CI = 0.39–0.90), and death 0.84 (95% CI = 0.65–1.11). In reduced‐dose patients (7,639 per arm), mean age 80 years, HRs for dabigatran vs. rivaroxaban were SSE 0.73 (95% CI = 0.59–0.94), MB 0.74 (95% CI = 0.57–0.96), and death 0.95 (95% CI = 0.83–1.09). In conclusion, at either dose, dabigatran had similar or better effectiveness than rivaroxaban but lower bleeding risk. Death rates were not different.
Thyroid nodule size calculated using ultrasound and gross pathology as predictors of cancer: A 23‐year retrospective study
Authors: Zhao Ling , Yan Huixian , Pang Ping , Fan Xiaojing , Jia Xiaomeng , Zang Li , Luo Yukun , Wang Fulin , Yang Guoqing , Gu Weijun , Du Jin , Wang Xianling , Lyu Zhaohui , Dou Jingtao , Mu Yiming
Published: November 2018

Background

Thyroid nodules are very common. Ultrasound (US) and fine needle aspiration (FNA) are both integral in cancer screening. This study investigated the concordance between thyroid nodule sizes measured by US and gross pathologic examination and their relationship with malignancy.

Methods

A retrospective design was used to select consecutive patients with proven carcinoma of the thyroid. The number and maximum diameter of nodules, rates and types of malignancy, as well as predictors of malignancy were determined.

Results

The 10 944 patients examined had 15 283 thyroid nodules, 44.6% of which were malignant. Of the 4449 nodules sampled by FNA and the 8748 not sampled by FNA, 76.5% and 30.5% were malignant, respectively. The sensitivity, specificity, positive and negative predictive values (NPVs), and overall accuracy of FNA based on final pathology were 97.9%, 96.3%, 98.8%, 93.5%, and 97.5%, respectively. Nodule sizes determined by US were comparable with most nodules having either the same size range (n = 2959, 77.7%) or differing only by one size range (n = 770, 20.5%).

Conclusions

Thyroid nodule size is inversely related to malignancy risk, as larger nodules have lower malignancy rates. Nodule size estimated by US shows relatively good correlation with final pathologic size. However, thyroid nodules should undergo FNA regardless of size. If the FNA is not benign, nodule size should influence therapeutic decision making.