Enhanced catalytic activity of natural hematite-supported ppm levels of Pd in nitroarenes reduction

In this work, Pd NPs supported on amine-modified natural hematite have been prepared and characterized. Using this simple catalyst, nitroaromatic compounds as a major cause of industrial pollution were reduced to corresponding amines with ppm levels of Pd in the presence of designer surfactant TPGS-750-M and NaBH4 at room temperature in aqueous media. Synergistic effect between hematite and Pd is responsible for the observed enhanced catalytic activity. This catalyst was recycled for at least four times with a small decrease in the activity.The authors are grateful to Institute for Advanced Studies in Basic Sciences (IASBS) Research Council and Iran National Science Foundation (INSF-Grant number of 97021804) for support of this work. We also gratefully acknowledge financial support from the Spanish Ministerio de Economía y Competitividad (MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC), the Spanish Ministerio de Economía, Industria y Competitividad, Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER, EU) (projects CTQ2016-76782-P and CTQ2016-81797-REDC), the Generalitat Valenciana (PROMETEOII/2014/017) and the University of Alicante

Gold Nanoparticles Supported on Polyacrylamide Containing a Phosphorus Ligand as an Efficient Heterogeneous Catalyst for Three-Component Synthesis of Propargylamines in Water

Gold nanoparticles supported on a polyacrylamide containing a phosphinite ligand have been synthesized and characterized using different techniques such as TEM, SEM, EDX, XPS, and solid UV analyses. The new material was successfully applied as a heterogeneous catalyst for the three-component A3 coupling of amines, aldehydes, and alkynes to give propargylamines. Reactions are performed in neat water at 80 °C with only 0.05 mol% catalyst loading. The heterogeneous catalyst is recyclable during seven consecutive runs with small decrease in activity.The authors are grateful to Institute for Advanced Studies in Basic Sciences (IASBS) Research Council and Iran National Science Foundation (INSF-Grant number of 94010666) for support of this work. C. Nájera is also thankful to The Spanish Ministerio de Economia y Competitividad (MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC), FEDER, the Generalitat Valenciana (PROMETEOII/2014/017), and the University of Alicante for financial support

Magnetic nanoparticles supported oxime palladacycle as a highly efficient and separable catalyst for room temperature Suzuki–Miyaura coupling reaction in aqueous media

A novel magnetic nanoparticle-supported oxime palladacycle catalyst was successfully prepared and characterized. The magnetically recoverable catalyst was evaluated in the room temperature Suzuki–Miyaura cross-coupling reaction of aryl iodides and bromides in aqueous media. The catalyst was shown to be highly active under phosphine-free and low Pd loading (0.3 mol%) conditions. The catalyst could be easily separated from the reaction mixture using an external magnet and reused for six consecutive runs without significant loss of activity.The authors are grateful to Institute for Advanced Studies in Basic Sciences (IASBS) Research Council and Iran National Science Foundation (INSF-Grant number of 93020713) for support of this work

Magnetic crosslinked copoly(ionic liquid) nanohydrogel supported palladium nanoparticles as efficient catalysts for the selective aerobic oxidation of alcohols

Nowadays it is still a great sustainable processes challenge to produce efficient, selective and easy magnetic recovery and recycling catalysts for oxidation of alcohols using air as the oxidant. In this work, a new magnetic nanohydrogel comprising [DABCO-allyl][Br] ionic liquid, allyl alcohol and N,N'-methylenebis(acrylamide) is used for stabilization of small and highly uniform palladium nanoparticles of 3–4 nm size MXCPILNHG@Pd. This material has been characterized by Fourier-transform infrared spectroscopy (FTIR), atomic adsorption spectroscopy (AAS), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), SEM-Map, energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectra (XPS), vibrating-sample magnetometer (VSM) and dynamic light scattering (DLS). According to optimization of cross-linking degree and ratio of DABCO-IL, MXCPILNHG-2@Pd is found as a highly selective catalyst in oxidations of primary alcohols to the corresponding aldehydes in toluene and to acids in water. Furthermore, secondary alcohols were reacted efficiently to the corresponding ketones in both toluene and water. Catalyst is magnetically recovered and recycled for several times in both toluene and water and the reused catalysts are characterized by TEM and XPS.The authors are grateful to Institute for Advanced Studies in Basic Sciences (IASBS) Research Council, Zanjan University and Iran National Science Foundation (INSF-Grant number of 95,844,587) for support of this work. The authors are also thankful to the Spanish Ministerio de Economía, Industria y Competitividad, Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER, EU) (projects CTQ2016-76782-P and CTQ2016-81797-REDC), the Generalitat Valenciana (PROMETEOII/ 2014/017) and the University of Alicante

Applications of bimetallic PdCu catalysts

Bimetallic PdCu nanoparticles can be applied as catalysts in a wide range of chemical and electrochemical reactions. This review article overviews the preparation and synthetic applications of these bimetallic nanoparticles (BNPs) developed mainly over the last 20 years. These BNPs show better catalytic activity and selectivity than the monometallic counterparts due to their electronic and structural interactions. Simple general preparation methods include reduction of the corresponding salt precursors by different agents, solvothermal processes and galvanic replacement. In the case of supported catalysts, mainly wet impregnation and in situ reduction processes are used. In addition, these nanomaterials are prepared with different Pd/Cu compositions and with different morphologies. In the case of supported materials, many solid supports especially alumina, silica, titania, ceria, magnetite, zeolites, active carbon, graphene, carbon nanotubes, resins and polymers are employed allowing the recovery and reuse of the supported catalyst. In addition, the presence of copper reduces the economic cost of using palladium in industrial processes. Among several synthetic applications, C–C bond forming reactions such as Suzuki–Miyaura, Sonogashira–Hagihara, Heck–Mizoroki, Guerbet and A3-coupling are efficiently performed with PdCu BNPs. Reduction reactions under PdCu catalysis such as nitrate reduction for water purification, hydrodechlorination of organic pollutants, hydrogenation of CO2 and CO to methanol, semihydrogenation of alkynes to alkenes, and hydrogenation of C[double bond, length as m-dash]C double bonds, furfural to furfuryl alcohol, polyols, levulinic and succinic acids to lactones, styrene oxide to 2-phenylethanol and nitroaromatics to aromatic amines can be successfully performed. In the case of electrocatalytic reductions, oxygen reduction to water, CO2 reductions to CO, to alcohols, to hydrocarbons and to formate and hydrogen generation from water splitting can be highlighted. In the field of oxidation reactions using oxygen, CO can be transformed into CO2, alcohols into aldehydes, cyclopentene to cyclopentanone, ethylene and acetic acid to vinyl acetate, and aromatic compounds can be hydroxylated to phenols. Electrooxidation reactions are useful processes especially for direct alcohol and formic acid fuel cells. The oxygen-assisted water gas shift reaction can be efficiently performed under PdCu catalysis. In the field of chemical sensors, PdCu BNPs can detect hydrogen in low concentrations, liquefied petroleum gas, formaldehyde, glucose, thiocyanate and phenols. Other applications such as catalysts in hydrosilylation of acetylenes to vinylsilanes and the use of PdCu NPs as antimicrobial agents are also described.The authors are grateful to the Institute for Advanced Studies in Basic Sciences (IASBS) Research Council and Iran National Science Foundation (INSF-Grant number of 97016837) for support of this work. We also thank the Spanish Ministerio de Economía, Industria y Competitividad, Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER, EU) (projects CTQ2016-76782-P, CTQ2016-81797-REDC, and CTQ2017-85093-P), the Generalitat Valenciana (PROMETEOII/2014/017) and the University of Alicante for financial support

A fluorescence active catalyst support comprising carbon quantum dots and magnesium oxide doping for stabilization of palladium nanoparticles: Application as a recoverable catalyst for Suzuki reaction in water

Novel magnesium oxide-carbon quantum dots are synthesized and used for the formation and stabilization of palladium nanoparticles. This highly water dispersible material, Pd@MgO-CQD, has been used as an active catalyst for Suzuki coupling of aryl bromides at room temperature and aryl chlorides at 80 °C in water. Using fluorescence emission of the material, a new protocol for determining Pd loading and leaching in catalyst preparation and recycling process is developed.The authors are grateful to Institute for Advanced Studies in Basic Sciences (IASBS) Research Council and Iran National Science Foundation (INSF-Grant number of 94010666) for support of this work. C. Nájera is also thankful to the Spanish Ministerio de Economia y Competitividad (MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC), FEDER, the Generalitat Valenciana (PROMETEOII/2014/017) and the University of Alicante for financial support

Risk criteria classification and the evaluation of blasting operations in open pit mines by using the FDANP method

Purpose. Mineral projects are heavily influenced by risk factors. By providing evidence-based information and analysis to make informed decisions about how to choose between options, a risk assessment can be made. Methods. In this study, the relationships of 46 criteria and 10 dimensions affecting the risk of blasting operations were investigated in order to determine the significance, effectiveness, relative weight of the criteria and dimensions as well as to prioritize the risk criteria of blasting operations. For this purpose, the combination of the FDEMATEL method and FANP method are used as FDANP. Findings. The most important criterion is the lack of specialized knowledge (C1). The damage to manpower criterion (C46) will receive the greatest impact from other criteria. The criterion for implementing the explosion plan, without respecting the design principles (C12) has most interactions with other criteria and the failure to determine the amount of production capacity (low or high) criterion (C45) has the least interactions with other criteria. According to the FDANP method, the number of explosions in one stage (C14) is the first criterion of the blasting operations risk. Originality. By controlling this criterion, the effects and destructive consequences of blasting operations can be prevented. Controlling this criterion reduces the risk of blasting operations and also reduces the damage by C46 criterion. From comparison, human resources dimension (D1) is the most effective and natural hazards dimension (D10) has the greatest interactions with other dimensions and is most affected among the other dimensions. The production and extraction consideration dimension (D9) has the least interaction with other dimensions and is less important. Practical implications. By reducing the destructive effects of blasting operations, two favorable results will be achieved: the reduction of damage caused by undesirable consequences and the assignment of a greater share of blast energy to the desired outcomes.Мета. Розробка класифікації критеріїв оцінки ризиків на кар’єрах із використанням методу аналітичної мережі нечітких процесів прийняття рішень на основі фактичної інформації та її комплексного аналізу. Методика. В даному дослідженні були вивчені взаємозв’язки 46 критеріїв і 10 параметрів, що впливають на ризик вибухових робіт, з метою визначення значущості, ефективності, відносної ваги критеріїв та параметрів, а також визначення пріоритетності критеріїв ризику вибухових операцій. Для цього був використаний метод FDANP, який являє собою комбінацію методу FDEMATEL (Fuzzy Decision Making Trial and Evaluation Laboratory) і методу FANP. Результати. Встановлено, що в оцінці ризиків відсутність спеціалізованих знань (С1) є найбільш важливим критерієм. Відзначається, що критерій завданих збитків робочій силі (C46) відчуває найбільший вплив з боку інших критеріїв. Критерій виконання плану вибуху без урахування проектних принципів (C12) найбільше взаємодіє з іншими критеріями, а критерій нездатності визначення обсягу виробничої потужності (низький або високий) (C45) взаємодіє з іншими критеріями найменше. Згідно з методом FDANP, кількість вибухів на одній стадії (C14) є першим критерієм ризику вибухових робіт. При порівнянні параметрів виявлено, що людські ресурси (D1) є найбільш ефективним параметром, а стихійні лиха (D10) найсильніше взаємодіють з іншими параметрами та найбільш схильні до їх впливу. Визначено, що параметр впливу виробництва та видобутку (D9) менше всього взаємодіє з іншими параметрами і менш важливий. Наукова новизна. Науково обґрунтовані математичні взаємозв’язки між величинами ризику підривних робіт. Встановлено, що, контролюючи критерій (C14), можна запобігти руйнівним наслідкам вибухових робіт, а управління даним критерієм знижує ризики вибухових робіт, а також зменшує шкоду за критерієм C46. Практична значимість. Зменшення руйнівного впливу вибухових робіт може призвести до двох сприятливих результатів: скорочення збитку, викликаного небажаними наслідками вибуху, і спрямованому використанню більшої частки енергії вибухових робіт для отримання бажаних результатівЦель. Разработка классификации критериев оценки рисков на карьерах с использованием метода аналитической сети нечетких процессов принятия решений на основе фактической информации и ее комплексного анализа. Методика. В данном исследовании были изучены взаимосвязи 46 критериев и 10 параметров, влияющих на риск взрывных работ, с целью определения значимости, эффективности, относительного веса критериев и параметров, а также определения приоритетности критериев риска взрывных операций. Для этого был использован метод FDANP, который представляет собой комбинацию метода FDEMATEL (Fuzzy Decision Making Trial and Evaluation Laboratory) и метода FANP. Результаты. Установлено, что в оценке рисков отсутствие специализированных знаний (С1) является наиболее важным критерием. Отмечается, что критерий нанесенного ущерба рабочей силе (C46) испытывает наибольшее влияние со стороны других критериев. Критерий выполнения плана взрыва без учета проектных принципов (C12) больше всего взаимодействует с другими критериями, а критерий неспособности определения объема производственной мощности (низкий или высокий) (C45) взаимодействует с другими критериями меньше всего. Согласно методу FDANP, количество взрывов на одной стадии (C14) является первым критерием риска взрывных работ. При сравнении параметров выявлено, что человеческие ресурсы (D1) являются наиболее эффективным параметром, а стихийные бедствия (D10) сильнее всего взаимодействуют с другими параметрами и наиболее подвержены их влиянию. Определено, что параметр учета производства и добычи (D9) меньше всего взаимодействует с другими параметрами и менее важен. Научная новизна. Научно обоснованы математические взаимосвязи между величинами риска взрывных работ. Установлено, что, контролируя критерий (C14), можно предотвратить разрушительные последствия взрывных работ, а управление данным критерием снижает риски взрывных работ, а также уменьшает ущерб по критерию C46. Практическая значимость. Уменьшение разрушительного воздействия взрывных работ может привести к двум благоприятным результатам: сокращению ущерба, вызванного нежелательными последствиями взрыва, и направленному использованию большей доли энергии взрывных работ для получения желаемых результатов.The authors would like to thank Mining Engineering Department, Islamic Azad University (South Tehran Branch) for supporting this research

1-Butyl-3-methyl-2-(diphenylphosphino)imidazalolium hexafluorophosphate as an efficient ligand for recoverable palladium-catalyzed Suzuki-Miyaura reaction in neat water

The 1-butyl-3-methyl-2-(diphenylphosphino)imidazalolium hexafluorophosphate is prepared and used as a water-soluble ligand in the Suzuki-Miyaura reaction. This ligand and palladium chloride generates a new active catalyst for the Suzuki coupling reaction between aryl iodides or bromides with arylboronic acids in neat water. This catalyst can be recycled and reused for the coupling reaction of 4-bromobenzonitrile with phenylboronic acid for at least six runs with low decreasing in catalytic activity.The authors are grateful to Institute for Advanced Studies in Basic Sciences (IASBS) Research Council and Iran National Science Foundation (INSF-Grant number of 97021804) for support of this work. We also gratefully acknowledge financial support from the Spanish Ministerio de Ciencia e Innovaci on (MICINN) (projects CTQ2010-20387 and Consolider Ingenio 2010, CSD2007-00006), the Spanish Ministerio de Economía y Competitividad (MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC), the Spanish Ministerio de Economía, Industria y Competitividad, Agencia Estatal de Investigaci on (AEI) and Fondo Europeo de Desarrollo Regional (FEDER, EU) (projects CTQ2016-76782-P and CTQ2016-81797-REDC), the Generalitat Valenciana (PROMETEO2009/039 and PROMETEOII/2014/017), the University of Alicante

Synthesis of 5-heptadecyl- and 5-heptadec-8-enyl substituted 4-amino-1,2,4-triazole-3-thiol and 1,3,4-oxadiazole-2-thione from (Z)-octadec-9-enoic acid: preparation of Palladium(II) complexes and evaluation of their antimicrobial activity

Two 4-amino-1,2,4-triazoles and two 1,3,4-oxadiazoles are obtained in a common synthetic route including hydrogenation-hydrazidation of (Z)-methyl octadec-9-enoate to octadecanoic hydrazide under atmospheric air. Preservation of olefinic bond in heptadec-8-enyl group is achieved by carrying out hydrazidation reaction under the presence of an argon atmosphere. The disappearance of the olefinic bond is detected by physical data, IR, 1H, and13C NMR spectroscopy. New palladium complexes derived from 4-amino-5-heptadecyl-1,2,4-triazole-3-thiol and 5-heptadecyl-1,3,4-oxadiazole-2(3H)-thione are obtained and characterized by elemental analysis (solid state), IR, 1H, 13C NMR spectroscopy, XRD, and XPS. These resulting metallic entities are also identified in solution based in mass spectrometry (MS-ESI) experiments. Most compounds and their palladium(II) complexes are tested in vitro against Gram-positive, Gram-negative bacteria, and fungi, some of them showed variable activity.Financial support was provided by the Spanish Ministerio de Ciencia e Innovación (MICINN) (projects CTQ2010-20387, and Consolider-Ingenio 2010, CSD2007-00006), the Spanish Ministerio de Economía y Competitividad (MINECO) (projects CTQ2013-43446-P, and CTQ2014-51912-REDC), FEDER, the Generalitat Valenciana (PROMETEO 2009/039 and PROMETEOII/2014/017) and the University of Alicante. One of us (M.C.) thanks USTO-MB for scientific leave

The epidemiology of microbial agents related to patients with multiple sclerosis (MS)

     Multiple Sclerosis (MS) is one of the autoimmune diseases which affects the central nervous system and its etiology has not yet been identified. The disparity between youth and disability in reproductive ages is considered to be of particular importance for this disease and the need for research which illuminates various epidemiological, etiologic, clinical and therapeutic angles of multiple sclerosis is deeply felt. The purpose of this study is to consider the epidemiology of microbial agents related to patients with multiple sclerosis (MS). From 37 patients with multiple sclerosis according to the physician examination and McDonald criteria , serum samples were taken. Until testing, serum samples were stored in a freezer at -70 ° C. Subsequently, viral and bacterial agents were identified using specific primers and PCR method. In this study, the numbers of microbial agents were as the following: 7 retrovirus associated with MS (MRSV), 17 EBV, 8 HSV6, 11 JC virus, 10 CMV, 8 B19, 14Corona virus, 1 Helicobacter pylori, 15 Acinetobacter, 9 Borrelia burgdorferi, and 19 Chlamydia pneumonia. Identification of the relationship between different infectious agents in MS is necessary to prepare feasible data about tracing and treatment of MS related to these microorganisms that may be beneficial to clinicians to select a convenient empirical therapeutic diet in MS related to pathogens at the bedhead and can open up a new path to new therapeutic approaches.