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1.
Dalton Trans ; 53(8): 3654-3665, 2024 Feb 20.
Artículo en Inglés | MEDLINE | ID: mdl-38289280

RESUMEN

Two new metal-organic frameworks (MOFs), namely, {[Zn(HL)(bpea)]·DMF}n (Zn-MOF-1) and {[Co(HL)(bpea)]·DMF}n (Co-MOF-2) (H3L = 3-(3,5-dicarboxybenzyloxy)benzoic acid, bpea = 1,2-di(pyridyl)ethane), were obtained by the reaction of H3L and N-containing ligand bpea with Zn(NO3)2·6H2O and Co(NO3)2·6H2O, respectively. The isomorphic Zn-MOF-1 and Co-MOF-2 featured a 3D penetrating framework with different stabilities, luminescence, and catalytic properties. Luminescence measurement indicated that Zn-MOF-1 could be used to detect Al3+ through a turn-on effect with a detection limit of 0.42 µM. The sensing mechanism experiments showed that the enhanced luminescence of Zn-MOF-1 toward Al3+ may be due to the weak interaction between Al3+ and Zn-MOF-1 and the absorbance-caused enhancement (ACE) mechanism. Meanwhile, both Zn-MOF-1 and Co-MOF-2 showed interesting CO2 adsorption properties and could catalyze the cycloaddition of CO2 to epoxides resulting in 96 and 92% ideal products within 12 hours, respectively. They can be cycled up to 5 times without significant loss of catalytic efficiency.

3.
Altern Ther Health Med ; 29(8): 770-775, 2023 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-37708551

RESUMEN

Objective: This study aimed to investigate the clinical effectiveness of the SilverFlow branch stent through endovascular isolation and in situ fenestration (ISF) for the treatment of aortic dissection (AD) involving the aortic arch. Methods: A total of 21 patients with AD involving the aortic arch, admitted to our hospital between September 2021 and January 2023, were selected for this prospective study. All patients underwent treatment with an endoluminal isolated ISF-covered stent, with the branch stent being the SilverFlow, developed by Shenzhen Xianjian Company. We assessed the success rate of the ISF procedure stent-related complications and compared the volumes of the true and false cavities before and after treatment. Follow-up evaluations were conducted 1, 3, and 6 months post-operation, focusing on neurological complications, mortality, and the need for secondary interventional treatment. Results: Among the 21 AD patients with aortic arch involvement, 20 (95.23%) underwent non-emergency surgery, while 1 (4.76%) required emergency surgery due to cardiac ischemia and signs of dissection rupture. All surgeries were successfully completed. After treatment, the average volume of the true lumen significantly decreased compared to pre-treatment levels, while the volume of the false lumen significantly increased (P < .05). The success rate was 100%, with only one case (4.76%) experiencing type I internal leakage. There were no cases of stent displacement, distortion, or fenestration vessel occlusion. One patient (4.76%) succumbed to acute pericardial tamponade, resulting in a mortality rate of 4.76%. Another patient (4.76%) suffered from upper limb ischemia, significantly improving with antithrombotic drug treatment. No occurrences of stroke, visceral ischemia, or other complications were reported, and no secondary interventional treatments were required. Conclusions: The application of the SilverFlow branch stent for endovascular isolation of ISF in AD cases involving the aortic arch demonstrates a high success rate, low complication and mortality rates, and significant clinical feasibility and value.


Asunto(s)
Aneurisma de la Aorta Torácica , Disección Aórtica , Implantación de Prótesis Vascular , Humanos , Prótesis Vascular , Implantación de Prótesis Vascular/métodos , Estudios Prospectivos , Aneurisma de la Aorta Torácica/diagnóstico por imagen , Aneurisma de la Aorta Torácica/cirugía , Stents , Disección Aórtica/diagnóstico por imagen , Disección Aórtica/cirugía , Resultado del Tratamiento , Isquemia/cirugía , Estudios Retrospectivos
4.
Mol Phylogenet Evol ; 189: 107914, 2023 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-37666378

RESUMEN

Phylogenetic studies in the phylogenomics era have demonstrated that reticulate evolution greatly impedes the accuracy of phylogenetic inference, and consequently can obscure taxonomic treatments. However, the systematics community lacks a broadly applicable strategy for taxonomic delimitation in groups characterized by pervasive reticulate evolution. The red-fruit genus, Stranvaesia, provides an ideal model to examine the influence of reticulation on generic circumscription, particularly where hybridization and allopolyploidy dominate the evolutionary history. In this study, we conducted phylogenomic analyses integrating data from hundreds of single-copy nuclear (SCN) genes and plastomes, and interrogated nuclear paralogs to clarify the inter/intra-generic relationship of Stranvaesia and its allies in the framework of Maleae. Analyses of phylogenomic discord and phylogenetic networks showed that allopolyploidization and introgression promoted the origin and diversification of the Stranvaesia clade, a conclusion further bolstered by cytonuclear and gene tree discordance. With a well-inferred phylogenetic backbone, we propose an updated generic delimitation of Stranvaesia and introduce a new genus, Weniomeles. This new genus is distinguished by its purple-black fruits, thorns trunk and/or branches, and a distinctive fruit core anatomy characterized by multilocular separated by a layer of sclereids and a cluster of sclereids at the top of the locules. Through this study, we highlight a broadly-applicable workflow that underscores the significance of reticulate evolution analyses in shaping taxonomic revisions from phylogenomic data.


Asunto(s)
Sueños , Rosaceae , Filogenia , Rosaceae/genética
5.
PhytoKeys ; 229: 47-60, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-37457385

RESUMEN

Docynia has been treated as a separate genus or merged into Cydonia or Docyniopsis. Our phylogenomic evidence from 797 single-copy nuclear genes and plastomes confirmed the sister relationship between Docynia and Docyniopsis. By integrating the phylogenomic and morphological evidence, we propose to accept a broad generic concept of Malus and merge Docynia into Malus. Three new combinations are also made here: Malusdelavayi (Franch.) B.B.Liu, M.indica (Wall.) B.B.Liu and M.longiunguis (Q.Luo & J.L.Liu) B.B.Liu.

6.
Inorg Chem ; 62(19): 7324-7332, 2023 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-37130306

RESUMEN

Negative temperature coefficient (NTC) thermistors feature higher sensitivities and faster response speeds and thereby have particular applications in many fields. However, current NTC thermistors are mostly based on inorganic ceramic materials, which show obvious drawbacks in material synthesis, property modulation, and flexible film fabrication. Herein, we report, for the first time, the promising application of an inorganic-organic hybrid NTC thermistor. A new lead-free hybrid iodo bismuthate [1,1',1″-(benzene-1,3,5-triyl)tris(3-methyl-1H-imidazol-3-ium)]Bi2I9 [denoted as (Me3TMP)Bi2I9] was synthesized by a "double-free" strategy. (Me3TMP)Bi2I9 features a lead-free binuclear bismuth iodine anion charge compensated by a "classic hydrogen-bond-free" cation. (Me3TMP)Bi2I9 exhibits remarkable stability in water and UV light irradiation and shows the largest temperature sensitivity coefficient among all reported NTC materials. Theoretical calculation and detailed structural analysis disclose that the seriously distorted (BiI6) octahedra are responsible for the intriguing NTC effect for (Me3TMP)Bi2I9.

7.
Chem Commun (Camb) ; 58(17): 2858-2861, 2022 Feb 24.
Artículo en Inglés | MEDLINE | ID: mdl-35129567

RESUMEN

We report the thinnest copper sulfur atomic monolayer in an organic copper chalcogenide [Cu(CMP)]n (CMP = 5-chloro-2-mercaptopyridine). The layer features a new type of copper sulfur structure woven by both covalent bond and cuprophilic interaction and shows an intriguing oriented photoconductivity.

8.
Environ Pollut ; 290: 118119, 2021 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-34523528

RESUMEN

Although groundwater nitrogen pollution has been widely studied, the control of hydrogeological conditions on behavior of nitrogen compounds has been poorly understood. In this study, multiple stable isotopes (N/C/H/O), spectral characteristics of DOM coupled with water chemistry were used to reveal the sources and fate of nitrate and ammonium in three subareas with different hydrogeological conditions in the Central Yangtze River Basin. We identified three contrasting patterns of nitrogen sources and fate in groundwater controlled by different aquifer features. In a reducing porous aquifer mainly composed of carbonate minerals overlain by a thick low-permeability layer, the NH4-N concentration is high (mean 4.12 mg/L) but with quite low NO3-N concentration (mean 0.28 mg/L). The high ammonium is mainly from intense degradation of organic matter (OM), while denitrification at a higher rate results in nitrate removal. Feammox may be favored owing to abundant humics acting as the electron shuttle. In a weakly reducing to oxidizing porous aquifer mainly composed of aluminosilicate minerals overlain by a varying thickness of low-permeability layer, high ammonium occurs in a weakly reducing condition and is affected by both anthropogenic input and OM degradation, while high nitrate occurs in a more oxidizing condition and could be mainly from soil nitrogen, manure or sewage. Feammox may be also favored due to more acidic environment formed by weathering of aluminosilicate minerals, fluctuating redox condition and low abundance of labile organic carbon, while denitrification occurs at a slower rate coupled with concurrent re-oxidation of nitrite to nitrate. In an oxidizing porous - fissured aquifer system overlain by a thin low-permeability layer, the concentrations of ammonium and nitrate are both low, possibly due to strong hydrodynamic and flushing condition, although slightly higher concentration of nitrate exhibit similar sources and fate with the weakly reducing to oxidizing porous aquifer mentioned above.


Asunto(s)
Agua Subterránea , Contaminantes Químicos del Agua , Monitoreo del Ambiente , Nitratos/análisis , Nitrógeno/análisis , Compuestos de Nitrógeno , Isótopos de Nitrógeno/análisis , Ríos , Contaminantes Químicos del Agua/análisis
9.
Mitochondrial DNA B Resour ; 5(1): 798-799, 2020 Jan 24.
Artículo en Inglés | MEDLINE | ID: mdl-33366756

RESUMEN

The chloroplast genome of the Magnolia species from Central America has never been reported. With its local use for food flavoring, medicine, and wood, M. mexicana has been of good economic importance. In the present study, the complete chloroplast genome of M. mexicana was assembled via the genome skimming data. As a typical quadripartite structure, the plastome of M. mexicana with 159,906 bp in length includes two inverted repeats (26,554 bp) separated by a small single copy region (18,761 bp) as well as a large single copy region (88,037 bp). This chloroplast genome consists of 131 different genes, including 86 protein coding genes (CDS), eight rRNA genes, and 37 tRNA genes. The maximum likelihood phylogenetic analysis showed that M. mexicana from Central America was closely related to an evergreen species, M. odoratissima from East Asia.

10.
ACS Appl Mater Interfaces ; 12(49): 54694-54702, 2020 Dec 09.
Artículo en Inglés | MEDLINE | ID: mdl-33216521

RESUMEN

The employment of hybrid perovskite MAPbX3 (MA = CH3NH3+, X = Br or I) as photocatalysts in a photocatalytic hydrogen evolution reaction represents a promising approach to store solar energy. However, the toxicity of Pb makes these materials difficult to pass environmental evaluation while the intrinsic moisture sensitivity puts forward high anhydrous requirements in photocatalysts synthesis, storage, and application, which further reduces their service life. Herein, we demonstrate a hydrogen-bond-free strategy to synthesize moisture-stable hypotoxic hybrid perovskite for photocatalytic application by replacing traditional protonated countercations with alkylated countercations in a Pb-free hybrid system, which prevents water eroding hybrid perovskites via strong hydrogen bonds. A zero-dimensional Bi-based perovskite (3-ethylbenzo[d]thiazol-3-ium)4Bi2I10 (EtbtBi2I10) was synthesized, which contains dimeric (Bi2I10)4- formed by edge-sharing (BiI6) octahedra being different from the binuclear cluster in widely studied MA3Bi2I9. Theoretical calculations indicate that the electron communication between inorganic and organic moieties is responsible for its broadband absorption with a narrow band gap of 2.04 eV. EtbtBi2I10 exhibits excellent stability in distilled water, moisture air, acid solution, and UV-light irradiation. It shows effective photocatalytic performance in HI splitting to generate hydrogen with the performance comparable with MAPbI3. Introducing electron and hole-transporting channels drastically enhances the photocatalytic reaction.

11.
PhytoKeys ; 139: 99-118, 2020.
Artículo en Inglés | MEDLINE | ID: mdl-32089637

RESUMEN

As part of a comprehensive systematic study on the genus Eriobotrya and its close relatives from the E & SE Asia, new typifications of 23 names are presented here, along with some nomenclatural notes of the names involved. We lectotypified 22 names including accepted names and synonyms. They are: E. acuminatissima, E. bengalensis var. angustifolia; E. bengalensis f. intermedia, E. brackloi, E. brackloi var. atrichophylla, E. elliptica var. petelotii, E. fragrans var. furfuracea, E. glabrescens, E. grandiflora, E. henryi, E. oblongifolia, E. petiolata, E. platyphylla, E. poilanei, E. prinoides, E. prinoides var. laotica, E. salwinensis, E. serrata, E. stipularis, Hiptage cavaleriei, Photinia longifolia, Symplocos seguinii. One neotype of Photinia dubia was also proposed in this study, and E. pseudoraphiolepis and Mespilus cuila were identified as superfluous names. In addition, we also summarized the typification of 18 names for taxonomic reference: E. angustissima, E. balgooyi, E. condaoensis, E. × daduheensis, E. elliptica, E. fulvicoma, E. fragrans, E. glabrescens var. victoriensis, E. hookeriana, E. latifolia, E. obovata, E. malipoensis, E. merguiensis, E. tengyuehensis, E. wardii, Mespilus bengalensis, Photinia deflexa, and M. japonica.

12.
ChemSusChem ; 13(10): 2671-2676, 2020 May 22.
Artículo en Inglés | MEDLINE | ID: mdl-31965761

RESUMEN

Great efforts have been made to understand and upgrade the kinetically sluggish oxygen evolution reaction (OER). In this study, a series of V-doped LaCoO3 (V-LCO) OER electrocatalysts with optimized d-band centers are fabricated. When utilized as an electrode for the OER, as-formed LaCo0.8 V0.2 O3 (V-LCO-II) requires an overpotential of only 306 mV to drive a geometrical catalytic current density of 10 mA cm-2 . Furthermore, at a given overpotential of 350 mV, the OER current density of V-LCO-II is about 22 times that of pure LaCoO3 (LCO) nanoparticles. Tailoring of the d-band center by V doping facilitates the adsorption of OER intermediates and promotes the formation of amorphous active species on the surface of LCO through the exchange interaction between high-spin V4+ and low-spin Co2+ . This work may create new opportunities for developing other highly active OER catalysts through d-band center engineering.

13.
RSC Adv ; 10(17): 10023-10029, 2020 Mar 06.
Artículo en Inglés | MEDLINE | ID: mdl-35498579

RESUMEN

Compared with nanoscale quantum dots (QDs), the large-sized perovskite crystals not only possess better stability but also are convenient for application exploration. Herein, we develop a facile and efficient antisolvent vapor-assisted recrystallization approach for the synthesis of large-sized Cs4PbBr6 perovskite crystal microplates. In this method, for the first time, the shale-like Cs4PbBr6 microplates with lateral dimensions of hundreds of microns are fabricated by employing cetyltriethylammnonium bromide (CTAB) as a morphology-directing agent. FESEM, TEM, and AFM characterizations indicate that the as-obtained shale-like Cs4PbBr6 microplates are actually formed by 6-8 nm thick Cs4PbBr6 nanosheets with orientational stacking. Importantly, such highly crystalline Cs4PbBr6 microplates with shale-like morphology exhibit a narrow and intense green PL emission with a 59% PL quantum yield. Moreover, the planar structure of shale-like Cs4PbBr6 microplates makes it easy to form a preferred orientation on a substrate, which endow them with promising potential in optoelectronic devices such as lighting and displays.

14.
Chempluschem ; 84(7): 828-837, 2019 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-31943988

RESUMEN

Bismuth oxychloride ultrathin nanoplates (BiOCl-UTNs) are highly active, but their preparation are limited to closed-vessel hydrothermal and solvothermal techniques at high temperatures (110-180 °C). Here we report a straightforward poly(sodium 4-styrenesulfonate) (PSS)-mediated route for the large-scale synthesis of BiOCl-UTNs at room-temperature. In an open vessel, 6.15 g of BiOCl-UTNs with 3-5 nm thickness, and planar dimensions of 30-50 nm were produced. The strong electrostatic interaction between PSS and [Bi2 O2 ]2+ layers inhibited the growth rate of BiOCl nanoplates along <001> direction, and Na+ ions governed the electrolyte sedimentation to produce BiOCl-UTNs. The resulting BiOCl-UTNs exhibited high photocatalytic activity for the degradation of antibiotics and organic dyes because of their large specific surface area, increased light absorption ability, and fast separation and transfer efficiency of the photoexcited charge carriers.

15.
Front Plant Sci ; 10: 1731, 2019.
Artículo en Inglés | MEDLINE | ID: mdl-32117331

RESUMEN

The Eriobotrya-Rhaphiolepis (ER) clade consists of about 46 species distributed in East and Southeast Asia. Although Eriobotrya and Rhaphiolepis have been supported to form a clade, the monophyly of Eriobotrya and Rhaphiolepis at the genus level has never been well tested and their phylogenetic positions in Maleae still remain uncertain. This study aims to reconstruct a robust phylogeny of the ER clade in the framework of Maleae with a broad taxon sampling and clarify the phylogenetic relationship between Eriobotrya and Rhaphiolepis. This study employed sequences of the whole plastome (WP) and entire nuclear ribosomal DNA (nrDNA) repeats assembled from the genome skimming approach and included 83 samples representing 76 species in 32 genera of Rosaceae, especially Maleae. The Maximum Likelihood (ML) and Bayesian Analysis (BI) based on three datasets, i.e., WP, coding sequences of plastome (CDS), and nrDNA, strongly supported the paraphyly of Eriobotrya, within which Rhaphiolepis was nested. Our plastid tree supported the sister relationship between the ER clade and Heteromeles, and the nrDNA tree, however, did not resolve the phylogenetic placement of the ER clade in Maleae. Strong incongruence between the plastid and the nuclear trees is most likely explained by hybridization events, which may have played an important role in the evolutionary history of the ER clade. Molecular, morphological, and geographic evidence all supports the merge of Eriobotrya with Rhaphiolepis, which has the nomenclatural priority. We herein transferred 36 taxa of Eriobotrya to Rhaphiolepis. We also proposed a new name, Rhaphiolepis loquata B.B.Liu & J.Wen, for the economically important loquat, as the specific epithet "japonica" was pre-occupied in Rhaphiolepis.

16.
Dalton Trans ; 47(7): 2306-2317, 2018 Feb 13.
Artículo en Inglés | MEDLINE | ID: mdl-29367993

RESUMEN

Although great progress has been made in hybrid iodocuprates(i) as lighting phosphors, the effects of aromatic and aliphatic structure directing agents (SDAs) on their water stability, structure and photoluminescence (PL) properties are still not clear. Herein, aromatic N-heterocyclic 1,2-di(4-pyridyl)ethylene (dpe), aliphatic N-heterocyclic 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu) and N-aminoethylpiperazine (app) were selected to be SDAs to construct two types of hybrid iodocuprates(i) via a facile in situ approach. Aromatic dpe-derived cations are successfully directed to form (Me2dpe)(CuI3) (1), (Me2dpe)n(Cu4I6)n (2), (Et2dpe)2(Cu6I10) (3), and (H2dpe)n(Cu2I4)n (4). Three of them contain unprecedented inorganic iodocuprate clusters or chains. The aliphatic N-heterocyclic dbu- and app-derivative cations are responsible for the formation of (Hdbu)n(Cu2I3)n (5) and (H3app)2(Cu2I6)·2I·2H2O (6), which contain a (Cu2I3)- chain and a (Cu2I6)4- binuclear cluster, respectively. For the first time, the influence mechanisms of the water stabilities of iodocuprate-based PL materials were disclosed, by analyzing the possible interactions between SDAs and water molecules. 1-2 are PL silent due to their "self-quenching effect". 3, 4 and5 exhibit bright red, orange and yellow solid-state PL emissions at room temperature respectively, originating from the charge transfer between inorganic iodocuprate species and organic N-heterocycles. The co-template approach leads to multiple charge transfers in 6, which features a tunable PL behavior from bluish green to white by varying the excitation light, and has a quantum yield up to 43% (the highest value among hybrid iodocuprates containing (Cu2I6)4- clusters). The comparative study not only helps us to rationally synthesize iodocuprate-based PL materials with enhanced performance, but also provides a new method to obtain wavelength-dependent PL materials.

17.
Dalton Trans ; 46(37): 12474-12486, 2017 Sep 26.
Artículo en Inglés | MEDLINE | ID: mdl-28894867

RESUMEN

Two types of in situ formed structure directing agents (SDAs) including aromatic triphenylphosphine (PPh3)- and aliphatic piperazine (H2pp)-derivative cations were used to synthesize five new hybrid iodoargentates, namely (EtPPh3)Ag3I4 (1, Et = ethyl), (n-PrPPh3)Ag3I4 (2, n-Pr = n-propyl), (i-PrPPh3)Ag5I6 (3, i-Pr = isopropyl), (Me4pp)0.5AgI2 (4, Me = methyl), and (H3app)2(Ag2I6)·2I·2H2O (5, app = N-aminoethylpiperazine). A comparative study of the two types of SDAs on the structures, stabilities and properties of hybrid iodoargentates was performed in detail. Structurally, except for (EtPPh3)+ and (n-PrPPh3)+, which both directly form (Ag3I4)- anionic chains in 1 and 2, three SDAs generate hybrid iodoargentates different from each other with inorganic anions ranging from a 0-D (Ag2I6)4- dimer to 1-D α-type (AgI2)- and (Ag5I6)- chains. With regard to the electronic structures, aromatic PPh3-derivative cations make noticeable contributions to the bottom of the conduction bands, while aliphatic pp-derivative cations make nearly no contribution to the frontier orbitals, clearly indicating their different ways to adjust the band gaps. With regard to stability, the decomposition temperatures of 1-3 in the range of 324-349 °C are noticeably higher than the values of 217 and 225 °C for 4 and 5. Furthermore, 1-4 exhibit good water stabilities, which is ascribed to the alkylation reactions precluding the formation of strong hydrogen bonds between alkylated SDAs and extraneous H2O molecules. Contrarily, the presence of typical hydrophilic [double bond, length as m-dash]NH2+, [triple bond, length as m-dash]NH+ and -NH3+ groups on the protonated (H3app)3+ cation makes 5 sensitive to water and a hydrolysis reaction occurs to generate a cubic AgI phase. Finally, 1-3 exhibit high photocatalytic efficiencies for the degradation of rhodamine B (RhB) dye in wastewater under visible light. All conclusions obtained here will help a lot in the synthesis of stable functional metal halide-based hybrids.

18.
Inorg Chem ; 56(4): 1906-1918, 2017 Feb 20.
Artículo en Inglés | MEDLINE | ID: mdl-28169534

RESUMEN

In situ alkylation or protonation reactions on the thiazolyl-N donors of benzothiazole (btz) and its derivative 2-aminobenzothiazole (abtz) occurred to form four structure directing agents (SDAs), which feature different structure directing abilities and hydrophobicities. The thiazolyl-N alkylated and protonated btz cations direct to form an α-type (AgI2)- iodoargentate chain in (Etbtz)(AgI2) (1), (Prbtz)(AgI2) (2), and (Hbtz)(AgI2) (3), respectively, while the thiazolyl-N protonated abtz cation directs to form a new type of (Ag2I3)- anionic chain in (Habtz)(Ag2I3) (4). Compounds 1 and 4 represent the first noncentrosymmetric (NCS) hybrid iodoargentates with organic S-containing N-heterocycle derivative cations as SDAs. Further, 1 exhibits high water stability and is second harmonic generation (SHG) active with a response about twice that of KDP (KH2PO4). Importantly, the water stability studies indicate that hybrid iodoargentates with hydrophobic N-alkylated SDAs are more stable in water than those with relative hydrophilic N-protonated SDAs.

19.
Dalton Trans ; 45(47): 19062-19071, 2016 Dec 21.
Artículo en Inglés | MEDLINE | ID: mdl-27858012

RESUMEN

Solvothermal reactions of AgI with the vulcanization accelerator 2,2'-dibenzothiazolyl disulfide and hydroiodic acid in alcohols afford two hybrid iodoargentates with one-dimensional structures, namely (Et2mbt)[Ag2I3] (1, Hmbt = 2-mercaptobenzothiazole) and {(Hmbt)[AgI]}n (2). The syntheses of both 1 and 2 involve unprecedented multiple in situ reactions. Specifically, a simultaneous disulfide bond cleavage, N and S donor atoms bialkylation, and self-assembly reaction lead to 1 that contains a discrete N,S-biethylated cation (Et2mbt)+ and a rare inorganic (Ag2I3)- anionic chain, while a simultaneous disulfide bond cleavage, N-protonation and self-assembly reaction affords 2 which features zwitterionic Hmbt molecules coordinating with the opposite side Ag atoms of a neutral inorganic (AgI)n chain via forming Ag-S coordination bonds. The simultaneous alkylation on a thiazolyl-N donor and a thiol-S donor atom for a thiazolyl-based heterocycle using inexpensive alcohols and haloids under solvothermal conditions instead of traditional two-step organic synthesis was found for the first time. The two compounds have band gaps of 2.95 eV for 1, and 2.78 eV for 2 exhibiting an observed blue shift compared with bulk AgI. Also, 1 and 2 can be used as effective heterogeneous photocatalysts for methyl orange dye treatment under UV light irradiation.

20.
Dalton Trans ; 44(43): 18882-92, 2015 Nov 21.
Artículo en Inglés | MEDLINE | ID: mdl-26465876

RESUMEN

Two novel metal-organic frameworks (MOFs) [Cd3(padc)(Hpadc)(H2padc)(H2O)]n·nH2O (1, H3padc = pyrazole-3,5-dicarboxylic acid) and [Co4(pidc)2(Hpidc)4(H2O)3]n·12nH2O (2, H2pidc = pyridine-2,5-dicarboxylic acid), that both crystallize in polar space groups, were solvothermally synthesized by using achiral N,O-coordinated ligands. Compound 1 consists of trinuclear Cd(II)-based units that are further bridged by the backbone of H3padc ligands to form a three-dimensional (3-D) (4,6)-connected fsc topology network, while compound 2 features two types of double-helical tubes with different chiralities connecting with each other alternatively to construct a typical 2-D (3,6)-connected kgd topology network. Importantly, 1 exhibits combined properties of photoluminescence (PL) and second harmonic generation (SHG), and represents the first noncentrosymmetric H3padc-based MOF that was obtained without any ancillary ligands. While 2 shows strong antiferromagnetic interactions between paramagnetic Co(II) centers, and the aqueous solution of 2 exhibits effective homogeneous photocatalysis properties under visible irradiation. Further, the mechanisms of the physical properties of 1 and 2 are discussed in detail.

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