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1.
Nano Lett ; 24(17): 5224-5230, 2024 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-38640250

RESUMEN

Molecular devices that have an anisotropic periodic potential landscape can be operated as Brownian motors. When the potential landscape is cyclically switched with an external force, such devices can harness random Brownian fluctuations to generate a directed motion. Recently, directed Brownian motor-like rotatory movement was demonstrated with an electrically switched DNA origami rotor with designed ratchet-like obstacles. Here, we demonstrate that the intrinsic anisotropy of DNA origami rotors is also sufficient to result in motor movement. We show that for low amplitudes of an external switching field, such devices operate as Brownian motors, while at higher amplitudes, they behave deterministically as overdamped electrical motors. We characterize the amplitude and frequency dependence of the movements, showing that after an initial steep rise, the angular speed peaks and drops for excessive driving amplitudes and frequencies. The rotor movement can be well described by a simple stochastic model of the system.


Asunto(s)
ADN , ADN/química , Anisotropía , Movimiento (Física)
2.
J Phys Chem B ; 127(50): 10710-10722, 2023 Dec 21.
Artículo en Inglés | MEDLINE | ID: mdl-38060372

RESUMEN

DNA nanotechnology has enabled the creation of supramolecular machines, whose shape and function are inspired from traditional mechanical engineering as well as from biological examples. As DNA inherently is a highly charged biopolymer, the external application of electric fields provides a versatile, computer-programmable way to control the movement of DNA-based machines. However, the details of the electrohydrodynamic interactions underlying the electrical manipulation of these machines are complex, as the influence of their intrinsic charge, the surrounding cloud of counterions, and the effect of electrokinetic fluid flow have to be taken into account. In this work, we identify the relevant effects involved in this actuation mechanism by determining the electric response of an established DNA-based nanorobotic arm to varying design and operation parameters. Borrowing an approach from single-molecule biophysics, we determined the electrical torque exerted on the nanorobotic arms by analyzing their thermal fluctuations when oriented in an electric field. We analyze the influence of various experimental and design parameters on the "actuatability" of the nanostructures and optimize the generated torque according to these parameters. Our findings give insight into the physical processes involved in the actuation mechanism and provide general guidelines that aid in designing and efficiently operating electrically driven nanorobotic devices made from DNA.


Asunto(s)
ADN , Nanoestructuras , ADN/química , Nanoestructuras/química , Nanotecnología , Torque
3.
Environ Sci Technol ; 57(40): 15162-15172, 2023 Oct 10.
Artículo en Inglés | MEDLINE | ID: mdl-37756014

RESUMEN

Conventional monitoring systems for air quality, such as reference stations, provide reliable pollution data in urban settings but only at relatively low spatial density. This study explores the potential of low-cost sensor systems (LCSs) deployed at homes of residents to enhance the monitoring of urban air pollution caused by residential wood burning. We established a network of 28 Airly (Airly-GSM-1, SP. Z o.o., Poland) LCSs in Kristiansand, Norway, over two winters (2021-2022). To assess performance, a gravimetric Kleinfiltergerät measured the fine particle mass concentration (PM2.5) in the garden of one participant's house for 4 weeks. Results showed a sensor-to-reference correlation equal to 0.86 for raw PM2.5 measurements at daily resolution (bias/RMSE: 9.45/11.65 µg m-3). High-resolution air quality maps at a 100 m resolution were produced by combining the output of an air quality model (uEMEP) using data assimilation techniques with the network data that were corrected and calibrated by using a proposed five-step network data processing scheme. Leave-one-out cross-validation demonstrated that data assimilation reduced the model's RMSE, MAE, and bias by 44-56, 38-48, and 41-52%, respectively.

4.
Sci Data ; 10(1): 322, 2023 05 26.
Artículo en Inglés | MEDLINE | ID: mdl-37236985

RESUMEN

Low-cost air quality sensor systems can be deployed at high density, making them a significant candidate of complementary tools for improved air quality assessment. However, they still suffer from poor or unknown data quality. In this paper, we report on a unique dataset including the raw sensor data of quality-controlled sensor networks along with co-located reference data sets. Sensor data are collected using the AirSensEUR sensor system, including sensors to monitor NO, NO2, O3, CO, PM2.5, PM10, PM1, CO2 and meteorological parameters. In total, 85 sensor systems were deployed throughout a year in three European cities (Antwerp, Oslo and Zagreb), resulting in a dataset comprising different meteorological and ambient conditions. The main data collection included two co-location campaigns in different seasons at an Air Quality Monitoring Station (AQMS) in each city and a deployment at various locations in each city (also including locations at other AQMSs). The dataset consists of data files with sensor and reference data, and metadata files with description of locations, deployment dates and description of sensors and reference instruments.

5.
Eur J Mass Spectrom (Chichester) ; 29(2): 68-74, 2023 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-36437773

RESUMEN

A comparative mass spectrometric investigation using electrospray ionisation (ESI) and liquid injection field desorption/ionisation (LIFDI) techniques is reported for the highly luminescent and cationic copper cluster [(PCP)3Cu4]+ (1[Formula: see text], PCP = [1,3-(Ph2P)2C6H3]-). Depending on the available counter ion X-, ion pairs consisting of the original or a modified cluster cation and the weakly coordinating counter ion can be detected by LIFDI-high-resolution-mass spectrometry in addition to the cluster cation. Notably, only large counter ions with an extremely low tendency for metal coordination give rise to the observation of ion pairs, whereas smaller ions such as BF4- do not show peaks corresponding to ion pairs in their mass spectra. In principle, two pathways were identified for the formation of positively charged ion pairs: (i) association of a generated Cu+ ion to the neutral ion pair [(PCP)3Cu4]X (1+X, X- = BAr20F, BAr24F) and (ii) abstraction of an electron from the neutral ion pair [(PCP)3Cu4]X (1+X), leading to the oxidised ion pair [1+X][Formula: see text] (X- = Al(ORF)4).

6.
J Cancer Res Clin Oncol ; 149(9): 5493-5496, 2023 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-36469155

RESUMEN

With the increasing use of next-generation sequencing, highly effective targeted therapies have been emerging as treatment options for several cancer types. Recurrent gene-fusions have been recognized in sarcomas; however, options for targeted therapy remain scarce. Here, we describe a case of a sarcoma, associated with a RET::TRIM33-fusion gene with an exceptional response to a neoadjuvant therapy with the selective RET inhibitor selpercatinib. Resected tumor revealed subtotal histopathologic response. This is the first report of successful targeted therapy with selpercatinib in RET-fusion-associated sarcomas. As new targeted therapies are under development, similar treatment options may become available for sarcoma patients.


Asunto(s)
Neoplasias Pulmonares , Sarcoma , Neoplasias de los Tejidos Blandos , Humanos , Terapia Neoadyuvante , Pirazoles , Piridinas , Sarcoma/tratamiento farmacológico , Sarcoma/genética , Inhibidores de Proteínas Quinasas/uso terapéutico , Proteínas Proto-Oncogénicas c-ret/genética , Factores de Transcripción
7.
Dalton Trans ; 51(45): 17397-17404, 2022 Nov 21.
Artículo en Inglés | MEDLINE | ID: mdl-36325921

RESUMEN

A series of copper(I) and silver(I) complexes is reported containing the PCP-type tridentate ligand [(dppm)2CH]+ with a protonated carbodiphosphorane (CDPH) as cationic central donor group (dppm = 1,1-bis(diphenylphosphino)methane). In comparison to the previously reported gold complex [({dppm}2CH)AuCl]+ [Reitsamer et al., J. Organomet. Chem., 2017, 830, 150], the corresponding silver and copper complexes exhibit a κC-coordinated CDPH-group, which is absent in case of gold. For the series of silver complexes, we demonstrate that the κC-coordination of the CDPH-group is dependant on the ancillary ligand and that hydrogen bonding of the CDPH-group to the ancillary ligand can be competitive. The ability for such hydrogen bonding is a unique characteristic of protonated CDPs in comparison to other cationic ligands, which might offer benefits for applications in homogeneous catalysis by hemilability and substrate activation with this group.

8.
Biophys J ; 121(24): 4849-4859, 2022 12 20.
Artículo en Inglés | MEDLINE | ID: mdl-36071662

RESUMEN

Biomolecular nanomechanical devices are of great interest as tools for the processing and manipulation of molecules, thereby mimicking the function of nature's enzymes. DNA nanotechnology provides the capability to build molecular analogs of mechanical machine elements such as joints and hinges via sequence-programmable self-assembly, which are otherwise known from traditional mechanical engineering. Relative to their size, these molecular machine elements typically do not reach the same relative precision and reproducibility that we know from their macroscopic counterparts; however, as they are scaled down to molecular sizes, physical effects typically not considered by mechanical engineers such as Brownian motion, intramolecular forces, and the molecular roughness of the devices begin to dominate their behavior. In order to investigate the effect of different design choices on the roughness of the mechanical energy landscapes of DNA nanodevices in greater detail, we here study an exemplary DNA origami-based structure, a modularly designed rotor-stator arrangement, which resembles a rotatable nanorobotic arm. Using fluorescence tracking microscopy, we follow the motion of individual rotors and record their corresponding energy landscapes. We then utilize the modular construction of the device to exchange its constituent parts individually and systematically test the effect of different design variants on the movement patterns. This allows us to identify the design parameters that most strongly affect the shape of the energy landscapes of the systems. Taking into account these insights, we are able to create devices with significantly flatter energy landscapes, which translates to mechanical nanodevices with improved performance and behaviors more closely resembling those of their macroscopic counterparts.


Asunto(s)
ADN , Nanoestructuras , Reproducibilidad de los Resultados , Conformación de Ácido Nucleico , ADN/química , Nanotecnología , Fenómenos Físicos , Nanoestructuras/química
9.
Nature ; 607(7919): 492-498, 2022 07.
Artículo en Inglés | MEDLINE | ID: mdl-35859200

RESUMEN

To impart directionality to the motions of a molecular mechanism, one must overcome the random thermal forces that are ubiquitous on such small scales and in liquid solution at ambient temperature. In equilibrium without energy supply, directional motion cannot be sustained without violating the laws of thermodynamics. Under conditions away from thermodynamic equilibrium, directional motion may be achieved within the framework of Brownian ratchets, which are diffusive mechanisms that have broken inversion symmetry1-5. Ratcheting is thought to underpin the function of many natural biological motors, such as the F1F0-ATPase6-8, and it has been demonstrated experimentally in synthetic microscale systems (for example, to our knowledge, first in ref. 3) and also in artificial molecular motors created by organic chemical synthesis9-12. DNA nanotechnology13 has yielded a variety of nanoscale mechanisms, including pivots, hinges, crank sliders and rotary systems14-17, which can adopt different configurations, for example, triggered by strand-displacement reactions18,19 or by changing environmental parameters such as pH, ionic strength, temperature, external fields and by coupling their motions to those of natural motor proteins20-26. This previous work and considering low-Reynolds-number dynamics and inherent stochasticity27,28 led us to develop a nanoscale rotary motor built from DNA origami that is driven by ratcheting and whose mechanical capabilities approach those of biological motors such as F1F0-ATPase.


Asunto(s)
ADN , Difusión Facilitada , Proteínas Motoras Moleculares , ADN/química , Concentración de Iones de Hidrógeno , Proteínas Motoras Moleculares/química , Proteínas Motoras Moleculares/metabolismo , Movimiento (Física) , Movimiento , Concentración Osmolar , ATPasas de Translocación de Protón/química , ATPasas de Translocación de Protón/metabolismo , Procesos Estocásticos , Temperatura , Termodinámica
10.
Light Sci Appl ; 11(1): 90, 2022 Apr 08.
Artículo en Inglés | MEDLINE | ID: mdl-35396506

RESUMEN

The steady progress in medical diagnosis and treatment of diseases largely hinges on the steady development and improvement of modern imaging modalities. Raman spectroscopy has attracted increasing attention for clinical applications as it is label-free, non-invasive, and delivers molecular fingerprinting information of a sample. In combination with fiber optic probes, it also allows easy access to different body parts of a patient. However, image acquisition with fiber optic probes is currently not possible. Here, we introduce a fiber optic probe-based Raman imaging system for the real-time molecular virtual reality data visualization of chemical boundaries on a computer screen and the physical world. The approach is developed around a computer vision-based positional tracking system in conjunction with photometric stereo and augmented and mixed chemical reality, enabling molecular imaging and direct visualization of molecular boundaries of three-dimensional surfaces. The proposed approach achieves a spatial resolution of 0.5 mm in the transverse plane and a topology resolution of 0.6 mm, with a spectral sampling frequency of 10 Hz, and can be used to image large tissue areas in a few minutes, making it highly suitable for clinical tissue-boundary demarcation. A variety of applications on biological samples, i.e., distribution of pharmaceutical compounds, brain-tumor phantom, and various types of sarcoma have been characterized, showing that the system enables rapid and intuitive assessment of molecular boundaries.

11.
Nat Commun ; 11(1): 2131, 2020 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-32358505

RESUMEN

OLED technology beyond small or expensive devices requires light-emitters, luminophores, based on earth-abundant elements. Understanding and experimental verification of charge transfer in luminophores are needed for this development. An organometallic multicore Cu complex comprising Cu-C and Cu-P bonds represents an underexplored type of luminophore. To investigate the charge transfer and structural rearrangements in this material, we apply complementary pump-probe X-ray techniques: absorption, emission, and scattering including pump-probe measurements at the X-ray free-electron laser SwissFEL. We find that the excitation leads to charge movement from C- and P- coordinated Cu sites and from the phosphorus atoms to phenyl rings; the Cu core slightly rearranges with 0.05 Å increase of the shortest Cu-Cu distance. The use of a Cu cluster bonded to the ligands through C and P atoms is an efficient way to keep structural rigidity of luminophores. Obtained data can be used to verify computational methods for the development of luminophores.

12.
BMC Cancer ; 20(1): 351, 2020 Apr 25.
Artículo en Inglés | MEDLINE | ID: mdl-32334563

RESUMEN

BACKGROUND: The number of people living with soft-tissue and bone sarcomas is increasing due to improved individual therapy and changes in demographics. At present, there are no recommendations for psychological co-treatment, occupational and social reintegration following the treatment of soft tissue and bone sarcomas. METHODS: Seventy-four patients, 42 males and 32 females, aged between 18 and 80 years (54.58 ± 16.99 yr.) with soft-tissue (62) and bone sarcomas (12) were included to answer five standardized and one personal questionnaire regarding quality of life, function, reintegration and participation after surgical treatment. RESULTS: A number of tumour-specific and patient-specific factors were identified that affected the therapeutic outcome. Patients with sarcoma of the lower extremity described poorer mobility. Patients who underwent amputation reported a higher anxious preoccupation. Patients with a higher range of education were less fatalistic and avoiding. The size of tumours or additive radiation therapy did not affect the post-therapeutic quality of life, coping and function. There was a good correlation between anxiety and depression with occupational reintegration, function, quality of life and coping. CONCLUSION: Patients with sarcomas of the lower limb have a higher demand for postoperative rehabilitation and need more help in the postoperative occupational reintegration. Furthermore patients that underwent limb-preserving operations reported better postoperative function and quality of life. Risk assessment using patient-specific factors and an intensive psychological co-treatment may have a large role in the co-treatment of patients from the beginning of their cancer therapy.


Asunto(s)
Adaptación Psicológica , Amputación Quirúrgica/psicología , Amputación Quirúrgica/rehabilitación , Neoplasias Óseas/cirugía , Neoplasias de los Músculos/cirugía , Calidad de Vida , Reinserción al Trabajo/psicología , Adolescente , Adulto , Anciano , Anciano de 80 o más Años , Neoplasias Óseas/patología , Femenino , Estudios de Seguimiento , Humanos , Masculino , Persona de Mediana Edad , Neoplasias de los Músculos/patología , Osteosarcoma/patología , Osteosarcoma/cirugía , Pronóstico , Estudios Retrospectivos , Sarcoma/patología , Sarcoma/cirugía , Encuestas y Cuestionarios , Adulto Joven
13.
Sci Total Environ ; 720: 137577, 2020 Jun 10.
Artículo en Inglés | MEDLINE | ID: mdl-32325581

RESUMEN

We present a comprehensive study on the impacts and associated changes in costs resulting from the implementation of Environmental Speed Limits (ESLs), as a measure to reduce PM10 and associated health effects. We present detailed modelled emissions (i.e., CO2, NOx, PM2.5 and PM10), concentration levels (i.e., PM2.5 and PM10) and population exposure to PM2.5 and PM10 under three scenarios of ESL implementation for the Metropolitan Area of Oslo. We find that whilst emissions of NOx and CO2 do not seem to show significant changes with ESL implementation, PM10 emissions are reduced by 6-12% and annual concentration levels are reduced up to 8%, with a subsequent reduction in population exposure. The modelled data is used to carry out a detailed analysis to quantify the changes in private and social costs for the roads in Oslo where ESL are implemented today. This involves assessments related to human health, climate, fuel consumption, time losses and the incidence of traffic accidents. For a scenario using actual speed data from ESL implementation, our study shows a net benefit associated with the implementation of ESLs, whilst for a theoretical scenario with strict speed limit compliance we find a net increase in costs. This is largely due to variation in costs due to time losses between the scenarios, although uncertainties are high.

14.
Angew Chem Int Ed Engl ; 59(36): 15603-15609, 2020 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-32049402

RESUMEN

The dehydrogenation of organosilanes (Rx SiH4-x ) under the formation of Si-Si bonds is an intensively investigated process leading to oligo- or polysilanes. The reverse reaction is little studied. To date, the hydrogenolysis of Si-Si bonds requires very harsh conditions and is very unselective, leading to multiple side products. Herein, we describe a new catalytic hydrogenation of oligo- and polysilanes that is highly selective and proceeds under mild conditions. New low-valent nickel hydride complexes are used as catalysts and secondary silanes, RR'SiH2 , are obtained as products in high purity.

15.
Ultrasound Med Biol ; 46(5): 1082-1091, 2020 05.
Artículo en Inglés | MEDLINE | ID: mdl-32081584

RESUMEN

Assessment of the severity of internal carotid artery stenosis is relevant to therapeutic decisions. Direct measurement of stenosis in static three-dimensionally rendered ultrasonographic color-Doppler images after an orientation with 4-D gray-scale views (4D/3D-C-US) was recently observed to be metrically non-inferior to angiography. In the study described here, power-Doppler (Christian Doppler was a physicist) ultrasonography (4D/3D-P-US) was prospectively compared with angiography, 4D/3D-C-US and 2-D duplex ultrasonography (DUS) in a similar fashion using blinded observers. Percentage stenosis was measured in 36 patients. Continuous percentage stenosis measures (standard deviation of difference and concordance correlation coefficient) between angiography and 4D/3D-P-US did not differ from the results between angiography observers (p > 0.05). Dichotomous diagnosis with 4D/3D-P-US resulted in κ values similar to the inter-rater agreement of angiography and the inter-method agreement of 4D/3D-C-US and DUS compared with angiography. Binary accuracy did not differ between 4D/3D-P-US, 4D/3D-C-US and DUS (p > 0.5). In conclusion, stenosis grading using 4D/3D-P-US exhibited non-inferior inter-method agreement with angiography at good accuracies, similar to 4D/3D-C-US and DUS.


Asunto(s)
Estenosis Carotídea/diagnóstico por imagen , Ultrasonografía Doppler Dúplex/métodos , Ultrasonografía Doppler/métodos , Adulto , Anciano , Anciano de 80 o más Años , Velocidad del Flujo Sanguíneo , Estenosis Carotídea/fisiopatología , Angiografía Coronaria , Femenino , Humanos , Imagenología Tridimensional , Masculino , Persona de Mediana Edad
16.
Chemistry ; 26(6): 1335-1343, 2020 Jan 27.
Artículo en Inglés | MEDLINE | ID: mdl-31721322

RESUMEN

Derivatives of 1,2-dithienylethene (DTE) have superb photochromic properties due to an efficient reversible photocyclization reaction of their hexatriene structure and, thus, have application potential in materials for optoelectronics and (multi-responsive) molecular switches. Transition-metal complexes bearing switchable DTE motifs commonly incorporate their coordination site rather distant from the hexatriene system. In this work the redox active ligand 1,2-bis(2,5-dimethylthiophen-3-yl)ethane-1,2-dione is described, which reacts with [V(TMEDA)2 Cl2 ] to give a rare non-oxido vanadium(IV) species 3(M,M/P,P). This blue complex has two bidentate en-diolato ligands which chelate the VIV center and give rise to two five-membered metallacycles with the adjacent hexatriene DTE backbone bearing axial chirality. Upon irradiation with UVA light or prolonged heating in solution, the blue compound 3(M,M/P,P) converts into the purple atropisomer 4(para,M/para,P). Both complexes were isolated and structurally characterized by single-crystal X-ray diffraction analysis (using lab source and synchrotron radiation). The antiparallel configuration (M or P helicity) present in both 3(M,M/P,P) and 4(para,M/para,P) is a prerequisite for (reversible) 6π cyclization reactions. A CW EPR spectroscopic study reveals the metalloradical character for 3(M,M/P,P) and 4(para,M/para,P) and indicates dynamic reversible cyclization of the DTE backbone in complex 3(M,M/P,P) at ambient temperature in solution.

17.
Ultraschall Med ; 41(2): 167-174, 2020 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-31141825

RESUMEN

PURPOSE: The accuracy of internal carotid artery stenosis (ICAS) quantification depends on the method of stenosis measurement, impacting therapeutic decisions and outcomes. The NASCET method references the stenotic to the distal ICAS lumen, the ECST method to the local outer and the common carotid artery (CC) method to the CC diameter. Direct morphometric stenosis measurement with four-dimensionally guided three-dimensional ultrasonography (4D/3DC-US) demonstrated good validity for the commonly used NASCET method. The NASCET definition has clinically relevant drawbacks. Our purpose was to investigate the validity of the ECST and CC methods. MATERIALS AND METHODS: 4D/3DC-US percent-stenosis measures of 103 stenoses (80 patients) were compared to quantitative catheter angiography and duplex ultrasonography (DUS) in a blinded fashion. RESULTS: The 4D/3DC-US versus angiography intermethod standard deviation of differences (SDD, n = 103) was lower for the CC method (5.7 %) compared to the NASCET (8.1 %, p < 0.001) and ECST methods (9.1 %, p < 0.001). Additionally, it was lower than the NASCET angiography interrater SDD of 52 stenoses (SDD 7.2 %, p = 0.047) and non-inferior for the ECST method (p = 0.065). Interobserver analysis of equivalent grading methods showed no differences for the SDDs between angiography and 4D/3DC-US observers (p > 0.076). Binary comparison to angiography showed equal Kappa values > 0.7 and an accuracy ≥ 85 % for the NASCET and CC methods, higher than for the ECST method. The binary accuracy of ICAS grading did not differ from DUS for all methods. CONCLUSION: The new 4D/3DC-US CC method is an accurate and well reproducible alternative to the NASCET and ECST methods and offers potential for clinical application.


Asunto(s)
Estenosis Carotídea , Ultrasonografía Doppler , Angiografía , Arteria Carótida Común , Arteria Carótida Interna , Estenosis Carotídea/diagnóstico por imagen , Humanos , Ultrasonografía , Ultrasonografía Doppler/métodos
18.
J Am Chem Soc ; 142(1): 373-381, 2020 Jan 08.
Artículo en Inglés | MEDLINE | ID: mdl-31814392

RESUMEN

Organic light-emitting diodes (OLEDs) are revolutionizing display applications. In this aspect, luminescent complexes of precious metals such as iridium, platinum, or ruthenium still playing a significant role. Emissive compounds of earth-abundant copper with equivalent performance are desired for practical, large-scale applications such as solid-state lighting and displays. Copper(I)-based emitters are well-known to suffer from weak spin-orbit coupling and a high reorganization energy upon photoexcitation. Here we report a cationic organo-copper cluster [Cu4(PCP)3]+ (PCP = 2,6-(PPh2)2C6H3) that features suppressed nonradiative decays, giving rise to a robust narrow-band green luminophore with a photoluminescent (PL) efficiency up to 93%. PL decay kinetics corroborated by DFT calculations reveal a complex emission mechanism involving contributions of both thermally activated delayed fluorescence and phosphorescence. This robust compound was solution-processed into a thin film in prototype OLEDs with external quantum efficiency up to 11% and a narrow emission bandwidth (65 nm fwhm).

19.
Chemistry ; 26(1): 275-284, 2020 Jan 02.
Artículo en Inglés | MEDLINE | ID: mdl-31584732

RESUMEN

The reaction of 2,6-F2 C6 H3 SiMe3 with Ph2 PLi provided 2,6-(Ph2 P)2 C6 H3 SiMe3 (1), which can be regarded as precursor for the novel anionic tridentate ligand [2,6-(Ph2 P)2 C6 H3 ]- (PCP)- . The reaction of 1 with [AuCl(tht)] (tht=tetrahydrothiophene) afforded 2,6-(Ph2 PAuCl)2 C6 H3 SiMe3 (2). The subsequent reaction of 2 with CsF proceeded with elimination of Me3 SiF and yielded the neutral tetranuclear complex linear-[Au4 Cl2 (PCP)2 ] (3) comprising a string-like arrangement of four Au atoms. Upon chloride abstraction from 3 with NaBArF 4 (ArF =3,5-(CF3 )2 C6 H3 ) in the presence of tht, the formation of the dicationic tetranuclear complex linear-[Au4 (PCP)2 (tht)2 ](BArF 4 )2 (4) was observed, in which the string-like structural motif is retained. Irradiation of 4 with UV light triggered a facile rearrangement in solution giving rise to the dicationic tetranuclear complex cyclo-[Au4 (PCP)2 (tht)2 ](BArF 4 ) (5), which comprises a rhomboidal motif of four Au atoms. In 3-5, the Au atoms are associated by a number of significant aurophilic interactions. The atom-economic and selective reaction of 3 with HgCl2 yielded the neutral trinuclear bimetallic complex [HgAu2 Cl3 (PCP)] (6) comprising significant metallophilic interactions between the Au and Hg atoms. Therefore, 6 may be also regarded as a metallopincer complex [ClHg(AuCAu)] between HgII and the anionic tridentate ligand [2,6-(Ph2 PAuCl)2 C6 H3 ]- (AuCAu)- containing a central carbanionic binding site and two "gold-arms" contributing pincer-type chelation trough metallophilic interactions. Compounds 1-6 were characterized experimentally by multinuclear NMR spectroscopy and X-ray crystallography and computationally using a set of real-space bond indicators (RSBIs) derived from electron density (ED) methods including Atoms In Molecules (AIM), the Electron Localizability Indicator (ELI-D) as well as the Non-Covalent Interaction (NCI) Index.

20.
Clin Res Cardiol ; 109(5): 589-598, 2020 May.
Artículo en Inglés | MEDLINE | ID: mdl-31555985

RESUMEN

AIMS: Identifying factors associated with worse outcome following carotid endarterectomy (CEA) is important to improve prevention of major adverse cardiovascular and cerebrovascular events (MACCE), yet rarely used for registries. We intended to identify predictors of MACCE following CEA as recently analysed for stenting. METHODS AND RESULTS: Patients undergoing CEA at 2 centers over 13 years were entered into a database. Baseline clinical characteristics, procedural factors and a panel of clinical and lesion-related high-risk features (SHR) and exclusion criteria (SE), empirically compiled for stratification in the SAPPHIRE trial, were differentially analysed using Cox regressions. The analysis included 748 operations; 262 (35%) asymptomatic, 208 (28%) with previous strokes, and 278 (37%) with transient ischemic attacks (TIA). The overall 30-day MACCE rate was 6.7%, 5.0% in asymptomatic and 7.6% in symptomatic patients. Previous MI (HR 2.045, p = 0.022), diabetes (HR 2.111, p = 0.011) and symptomatic patients (HR 2.045, p = 0.044) were independently associated with MACCE. SE patients (n = 81) had a MACCE rate of 13.6%; the MACCE rate of the remainder dropped to 5.8% (4.7% in asymptomatic and 6.5% in symptomatic patients). Hazard ratio for SHR patients was 2.069 (CI 1.087-3.941) and 2.389 for SE (CI 1.223-4.666), each compared to all patients with lower risk and adjusted for symptomatic status. Among SHR and SE criteria NYHA 3-4, contralateral occlusions and intraluminal thrombus were significant determinants and MI < 4 weeks before CEA showed a strong trend (p = 0.05). CONCLUSION: Patients identified by SHR and SE criteria, prior MI and diabetes warrant increased attention to prevent MACCE following CEA.


Asunto(s)
Estenosis Carotídea/cirugía , Complicaciones de la Diabetes/complicaciones , Endarterectomía Carotidea/efectos adversos , Infarto del Miocardio/epidemiología , Complicaciones Posoperatorias/epidemiología , Accidente Cerebrovascular/epidemiología , Adulto , Anciano , Anciano de 80 o más Años , Estenosis Carotídea/complicaciones , Estudios de Cohortes , Femenino , Humanos , Modelos Logísticos , Masculino , Persona de Mediana Edad , Oportunidad Relativa , Sistema de Registros , Factores de Riesgo , Stents/efectos adversos , Resultado del Tratamiento
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