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1.
Eur Child Adolesc Psychiatry ; 33(1): 203-228, 2024 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-36757483

RESUMEN

The main objective of the review is to analyze the impact of the pandemic in children/teenagers with Autism spectrum disorder (ASD) and in their family environment. An electronic search was carried out in different databases (PsycInfo, Web of Science and Scopus) in order to find publications associated with the aim of this project. The search terms used were derived from the combination of the following search string: "((Pandemic OR Epidemic OR Outbreak OR COVID-19 OR Coronavirus) AND (Children OR Adolescents OR Youth OR Child OR Teenager) AND (Autism OR ASD OR Autism Spectrum Disorder))''. In total, 21 articles were included in this review. The findings of the different investigations included in this review show that the pandemic has produced a negative psychological impact in children/teenagers with ASD. Therefore, long-term follow-up studies should be carried out with the objective of creating effective interventions to treat this problematical.


Asunto(s)
Trastorno del Espectro Autista , COVID-19 , Niño , Adolescente , Humanos , COVID-19/epidemiología , Trastorno del Espectro Autista/epidemiología , Trastorno del Espectro Autista/terapia , Pandemias , Brotes de Enfermedades
2.
Psychol Res ; 87(4): 988-1011, 2023 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-35859072

RESUMEN

There is evidence to support the positive contribution of autobiographical recall based techniques on individuals' quality of life, mood and cognitive functioning. In this review, we analyzed the effects of the use of personal photographs in interventions based on autobiographical memory in older people with and without cognitive impairment. The PRISMA guidelines for systematic reviews were followed. The search was carried out in the electronic databases Web of Sciences (WOS), Medline (PubMed), SCIELO and PsycInfo (American Psychological Association). The articles based on clinical trials selected were evaluated using the PEDRo scale, which is specific to this type of article. Of the 1098 articles initially found, 6 met the inclusion criteria. The final articles focused their intervention on the use of autobiographical photographs as a means of stimulation. The results show that the use of photographs in different autobiographical recall stimulation techniques is associated with higher scores on well-being and quality of life, as well as with improvements in personal identity and cognitive functioning. This suggests that using personal photographs shows promise in enhancing the effect of these types of interventions in healthy or cognitively impaired older adults.


Asunto(s)
Disfunción Cognitiva , Calidad de Vida , Humanos , Anciano , Emociones , Cognición , Recuerdo Mental
3.
Food Microbiol ; 104: 103981, 2022 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-35287810

RESUMEN

Saccharomyces yeasts from different origins and species fermented in a semi-synthetic must containing aroma precursor of cv. Albariño and polyfunctional mercaptans precursors. The resulting wines were subjected to accelerate anoxic aging. Afterward, aroma profiles were analyzed by distinct gas chromatography methodologies. Cryotolerant strains showed better fermentation performances with significant differences in volatile and non-volatile fermentation products than Saccharomyces cerevisiae (S. cerevisiae). We suggested that the highest levels γ-butyrolactone and diethyl succinate in Saccharomyces uvarum (S. uvarum) strains, together with their substantial succinic acid yields, could be related to greater flux through the GABA shunt. These strains also had the highest production of ß-phenylethyl acetate, geraniol, and branched-chain ethyl esters. The latter compounds were highly increased by aging, while acetates and some terpenes decreased. S. kudriavzevii strains showed a remarkable ability to release polyfunctional mercaptans, with SK1 strain yielding up to 47-fold and 8-fold more 4-methyl-4-mercaptopentan-2-one (4MMP) than S. cerevisiae and S. uvarum strains, respectively. The wild S. cerevisiae beer isolate showed a particular aroma profile due to the highest production of ethyl 4-methylvalerate (lactic and fruity notes), γ-octalactone (coconut), and furfurylthiol (roasted coffee). The latter compound is possibly produced from the pentose phosphate pathway (PPP). Since erythritol, another PPP intermediate was largely produced by this strain.


Asunto(s)
Saccharomyces , Vino , Odorantes/análisis , Saccharomyces/metabolismo , Saccharomyces cerevisiae/metabolismo , Vino/análisis
4.
Phys Chem Chem Phys ; 23(18): 10845-10851, 2021 May 12.
Artículo en Inglés | MEDLINE | ID: mdl-33908516

RESUMEN

The on-surface synthesis of non-planar nanographenes is a challenging task. Herein, with the aid of bond-resolving scanning tunneling microscopy (BRSTM) and density functional theory (DFT) calculations, we present a systematic study aiming at the fabrication of corannulene-based nanographenes via intramolecular cyclodehydrogenation on a Au(111) surface. The formation of non-planar targeted products is confirmed to be energetically unfavorable compared to the formation of planar/quasi-planar undesired competing monomer products. In addition, the activation of intermolecular coupling further inhibits the formation of the final targeted product. Although it was not possible to access the corannulene moiety by means of on-surface synthesis, partial cyclodehydrogenation of the molecular precursors was demonstrated.

5.
Food Microbiol ; 97: 103763, 2021 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-33653514

RESUMEN

A collection of 33 Saccharomyces yeasts were used for wine fermentation with a sole nitrogen source: ammonium and four individual aroma-inducing amino acids. The fermentation performance and chemical wine composition were evaluated. The most valuable nitrogen sources were valine as a fermentation promoter on non-cerevisiae strains, phenylalanine as fruity aromas enhancer whereas the ethanol yield was lessened by leucine and isoleucine. S. cerevisiae SC03 and S. kudriavzevii SK02 strains showed to be the greatest producers of fruity ethyl esters while S. kudriavzevii strains SK06 and SK07 by shortening the fermentation duration. S. uvarum strains produced the greatest succinic acid amounts and, together with S. eubayanus, they reached the highest production of 2-phenylethanol and its acetate ester; whereas S. kudriavzevii strains were found to be positively related to high glycerol production.


Asunto(s)
Nitrógeno/metabolismo , Saccharomyces/metabolismo , Vino/microbiología , Etanol/metabolismo , Fermentación , Glicerol/metabolismo , Odorantes/análisis , Saccharomyces/clasificación , Saccharomyces/genética , Saccharomyces cerevisiae/clasificación , Saccharomyces cerevisiae/genética , Saccharomyces cerevisiae/metabolismo , Vino/análisis
6.
Angew Chem Int Ed Engl ; 60(50): 26346-26350, 2021 12 06.
Artículo en Inglés | MEDLINE | ID: mdl-34664770

RESUMEN

The Diels-Alder reaction is one of the most popular reactions in organic chemistry. However, its use in the field of on-surface synthesis is hampered by the spatial restrictions of this cycloaddition reaction. Herein we selected a cyclic strained triyne to demonstrate an on-surface hexadehydro-Diels-Alder reaction in a single molecule. The reaction was studied in detail by means of atomic force microscopy (AFM) with CO-functionalized tips. Our results pave the way to use this iconic pericyclic reaction for on-surface synthesis, introducing the concept of atom economy in the field.

7.
Acc Chem Res ; 52(9): 2472-2481, 2019 Sep 17.
Artículo en Inglés | MEDLINE | ID: mdl-31411855

RESUMEN

In recent years, synthetic transformations based on aryne chemistry have become particularly popular, mostly due to the spread of methods to generate these highly reactive intermediates in a controlled manner under mild reaction conditions. In fact, aryne cycloadditions such as the Diels-Alder reaction are nowadays widely used for the efficient preparation of polycyclic aromatic compounds. In 1998, our group discovered that arynes can undergo transition metal-catalyzed reactions, a finding that opened new perspectives in aryne chemistry. In particular, Pd-catalyzed [2 + 2 + 2] cycloaddition of arynes allowed the straightforward synthesis of triphenylene derivatives such as starphenes or cloverphenes. We found that this reaction is compatible with different substituents and sterically demanding arynes as starting materials. This transformation is especially useful to increase the molecular complexity in one single step, transforming molecules formed by n cycles in structures with 3n + 1 cycles. In fact, we took advantage of this protocol to prepare a large variety of sterically congested polycyclic aromatic hydrocarbons such as helicenes or twisted polyarenes. Soon after the discovery of the reaction, the co-cyclotrimerization of arynes with other reaction partners, such as electron deficient alkynes, significantly expanded the potential of this transformation. Also the use of catalysts based on alternative metals besides Pd (e.g., Ni, Cu, Au) or the use of other strained intermediates such as cycloalkynes or cycloallenes added value to this reaction. In addition, we realized that the Pd-catalyzed aryne cyclotrimerization reaction is particularly useful for the bottom-up preparation of well-defined nanographenes by chemical methods. Although the extreme insolubility of these planar nanographenes hampered their manipulation and characterization by conventional methods, recent advances in single molecule on-surface characterization by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) with functionalized tips under ultrahigh vacuum (UHV) conditions, permitted the impressive visualization of these nanographenes with submolecular resolution, together with the examination of the corresponding molecular orbital densities. Moreover, arynes have been shown to possess a rich on-surface chemistry. In particular, arynes have been generated and studied on-surface, showing that the reactivity is preserved even at cryogenic temperatures. On-surface aryne cyclotrimerization was also demonstrated to obtain large starphene derivatives. Therefore, it is expected that the combination of aryne cycloadditions and on-surface synthesis will provide notable findings in the near future, including the "à la carte" preparation of graphene materials or the synthesis of elusive molecules with unique properties.

8.
Clin Exp Rheumatol ; 38(4): 633-639, 2020.
Artículo en Inglés | MEDLINE | ID: mdl-31694754

RESUMEN

OBJECTIVES: Antinuclear antibodies (ANA) are fundamental in the diagnosis of systemic autoimmune rheumatic diseases (SARDs). Different assays for ANA screening are available, such as indirect immunofluorescence (IIF) on HEp-2 cells and Multiplex fluorescent immunoassay (MFI). This study aimed to clarify the importance of ANA detected only by IIF in the future development of SARDs and to recommend a laboratory algorithm that integrates the available diagnostic approaches to optimise the diagnosis of ANA IIF+MFI- subjects. METHODS: A total of 9,291 subjects with clinical suspicion of SARDs were evaluated for ANA by IIF and MFI. One hundred and ninety-eight subjects (2.1%) were ANA IIF+MFI-, who were followed up for 2 years. ANA were evaluated using IIF on HEp-2 cells and MFI on the BioPlex 2200. RESULTS: The ANA IIF+MFI- cohort included 106 subjects with SARDs, 26 subject with other autoimmune diseases (not-SARDs) and 66 subjects with minor symptoms or ANA requested in check-ups. Only 94 subjects underwent re-evaluation. After a 2-year follow-up, most re-evaluated subjects (51 patients) became ANA negative for both assays (mainly rheumatoid arthritis, polymyalgia and inflammatory bowel disease patients) and 35 subjects remained ANA IIF+MFI- (principally systemic sclerosis and systemic lupus erythematosus patients). A new algorithm for ANA evaluation was suggested. CONCLUSIONS: According to the proposed algorithm, ANA IIF+MFI- subjects should be screened by an alternative solid-phase assay such as line-immunoassay or ELISA.


Asunto(s)
Enfermedades Autoinmunes , Lupus Eritematoso Sistémico , Algoritmos , Anticuerpos Antinucleares , Técnica del Anticuerpo Fluorescente Indirecta , Humanos
9.
Psychogeriatrics ; 20(3): 310-320, 2020 May.
Artículo en Inglés | MEDLINE | ID: mdl-31881114

RESUMEN

BACKGROUND: Reminiscence functions in older adults have been associated with variables related to mental health such as depressive symptoms. Additionally, the way in which older adults cope with stress or their personality traits could influence their use of reminiscence. This study examined the relation between gender, coping styles, personality traits and reminiscence functions and how these variables predict depressive symptoms in institutionalised older adults. METHODS: The participants were 117 institutionalised older adults (range 62-98 years). They completed measures of reminiscence functions, depressive symptoms, coping styles and personality traits. RESULTS: Neuroticism and avoidance coping styles were related to a maladaptive use of reminiscence functions. The results showed that institutionalised older adults with high neuroticism and who usually use emotional discharge and logical analysis as avoidance coping styles and bitterness revival as a reminiscence function may be more likely to present depressive symptoms. CONCLUSION: The findings may help enhance the efficacy of interventions using reminiscence.


Asunto(s)
Adaptación Psicológica , Depresión/psicología , Emociones , Memoria/fisiología , Recuerdo Mental/fisiología , Personalidad , Anciano , Anciano de 80 o más Años , Estudios Transversales , Depresión/diagnóstico , Femenino , Hogares para Ancianos , Humanos , Masculino , Persona de Mediana Edad , Casas de Salud , Autoimagen , Encuestas y Cuestionarios
10.
Angew Chem Int Ed Engl ; 59(51): 22989-22993, 2020 Dec 14.
Artículo en Inglés | MEDLINE | ID: mdl-32845044

RESUMEN

Glaser-like coupling of terminal alkynes by thermal activation is extensively used in on-surface chemistry. Here we demonstrate an intramolecular version of this reaction performed by atom manipulation. We used voltage pulses from the tip to trigger a Glaser-like coupling between terminal alkyne carbons within a custom-synthesized precursor molecule adsorbed on bilayer NaCl on Cu(111). Different conformations of the precursor molecule and the product were characterized by molecular structure elucidation with atomic force microscopy and orbital density mapping with scanning tunneling microscopy, accompanied by density functional theory calculations. We revealed partially dehydrogenated intermediates, providing insight into the reaction pathway.

11.
J Am Chem Soc ; 141(39): 15488-15493, 2019 10 02.
Artículo en Inglés | MEDLINE | ID: mdl-31525873

RESUMEN

Four decades after the first (and only) reported synthesis of kekulene, this emblematic cycloarene has been obtained again through an improved route involving the construction of a key synthetic intermediate, 5,6,8,9-tetrahydrobenzo[m]tetraphene, by means of a double Diels-Alder reaction between styrene and a versatile benzodiyne synthon. Ultra-high-resolution AFM imaging of single molecules of kekulene and computational calculations provide additional support for a molecular structure with a significant degree of bond localization in accordance with the resonance structure predicted by the Clar model.

12.
Angew Chem Int Ed Engl ; 58(27): 9038-9042, 2019 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-31026104

RESUMEN

A route to generate cyclacenes by on-surface synthesis is explored. We started by synthesizing two tetraepoxycyclacenes by sequences of Diels-Alder cycloadditions. Subsequently, these molecules were deposited onto Cu(111) and scanning-tunneling-microscopy(STM)-based atom manipulation was employed to dissociate the oxygen atoms. Atomic force microscopy (AFM) with CO-functionalized tips enabled the detailed characterization of the reaction products and revealed that, at most, two oxygens per molecule could be removed. Importantly, our experimental results suggest that the generation of cyclacenes by the described route might be possible for larger epoxycyclacenes.

13.
Circulation ; 135(20): 1922-1934, 2017 05 16.
Artículo en Inglés | MEDLINE | ID: mdl-28249878

RESUMEN

BACKGROUND: Antiphospholipid syndrome is characterized by recurrent thrombosis and gestational morbidity in patients with antiphospholipid autoantibodies (aPLs). Predictive value of the presence of aPLs is low, and new markers are necessary to identify aPL carriers at higher risk and take preventive measures on them. The presence of circulating immune complexes of IgA bound to ß2-glycoprotein I (B2A-CIC) has been associated with occurrence of acute thrombotic events. In this work we study its possible predictive value for the appearance of acute thrombotic events in patients who are going to undergo transplant surgery, a well-known trigger of acute thrombotic events in aPL carriers. METHODS: We performed a follow-up study based on the Magnum 12+12 Cohort of patients who received a kidney transplant (n=1339). Three groups were established: group 1 patients who were positive for IgA anti-ß2-glycoprotein I (aB2GP1) and B2A-CIC (n=125); group 2 patients who were positive only for IgA aB2GP1 (n=240); and control group, patients who were negative for IgA aB2GP1 (n=974). Levels of autoantibodies and B2A-CIC were quantified immediately before the transplant surgery and patients were followed up for 6 months. RESULTS: In group 1, 46.4% of patients experienced any type of thrombosis versus 10.4% in group 2 (P<0.001) and 8.6% in the control group (P<0.001). The incidence of graft thrombosis in group 1 (31.2%) was significantly higher than that observed in group 2 (3.3%, P<0.001) and the control group (2.6%, P<0.001). In a multivariate analysis, the presence of B2A-CIC was an independent variable to experience any type of posttransplant thrombosis (hazard ratio, 6.72; 95% confidence interval, 4.81-9.37) and, prominently, for graft thrombosis (hazard ratio, 14.75; 95% confidence interval, 9.11-23.89). No significant differences were found between B2A-CIC-negative and control group patients. CONCLUSIONS: The presence of B2A-CIC is a predictor of acute thrombotic events. Patients who were positive for IgA aB2GP1 only are at risk of experiencing thrombosis if they are B2A-CIC positive. If they are B2A-CIC-negative patients, they have the same risk as the control group. Treatments to prevent acute thrombotic events should focus on B2A-CIC-positive patients.


Asunto(s)
Anticuerpos Antifosfolípidos/sangre , Complejo Antígeno-Anticuerpo/sangre , Inmunoglobulina A/sangre , Trasplante de Riñón/efectos adversos , Trombosis/sangre , beta 2 Glicoproteína I/sangre , Adulto , Anciano , Autoanticuerpos/sangre , Biomarcadores/sangre , Estudios de Cohortes , Femenino , Estudios de Seguimiento , Humanos , Trasplante de Riñón/tendencias , Masculino , Persona de Mediana Edad , Valor Predictivo de las Pruebas , Trombosis/diagnóstico , Trombosis/etiología
14.
J Am Chem Soc ; 140(26): 8156-8161, 2018 07 05.
Artículo en Inglés | MEDLINE | ID: mdl-29893120

RESUMEN

Here we present a new method that integrates atomic force microscopy (AFM) with analytical tools such as high-performance liquid chromatography (HPLC) with diode-array ultraviolet-visible (UV) absorbance, and mass spectrometry (MS) along with synthetic chemistry. This allows the detection, identification, and quantification of novel polycyclic aromatic hydrocarbons (PAH) in complex molecular mixtures. This multidisciplinary methodology is employed to characterize the supercritical pyrolysis products of n-decane, a model fuel. The pyrolysis experiments result in a complex mixture of both unsubstituted as well as highly methylated PAH. We demonstrate the AFM-driven discovery of a novel compound, benz[ l]indeno[1,2,3- cd]pyrene, with the chemical structure assignment serving as input for the chemical synthesis of such molecule. The synthesis is verified by AFM, and the synthesized compound is used as a reference standard in analytical measurements, establishing the first-ever unequivocal identification and quantification of this PAH as a fuel product. Moreover, the high-resolution AFM analysis detected several five- to eight-ring PAH, which represents novel fuel pyrolysis and/or combustion products. This work provides a route to develop new analytical standards by symbiotically using AFM, chemical synthesis, and modern analytical tools.

15.
Curr Opin Rheumatol ; 30(4): 361-364, 2018 07.
Artículo en Inglés | MEDLINE | ID: mdl-29401119

RESUMEN

PURPOSE OF REVIEW: The aim of this review is to summarize the recent studies regarding the relationship between anti-DFS70 antibodies and HIV-1 infection. Examining the interaction between HIV-1 integrate (HIV-IN) and DFS70 and its role in the integration into the host's chromatin. Then, summarizing the importance of anti-DFS70 autoantibodies binding the DFS70 in the same region as the HIV-IN. RECENT FINDINGS: The interaction between HIV-IN and DFS70 protein could be a proficient target in the treatment against HIV-1 infection. The blockade of DFS70 is more effective than the blockade of HIV-IN as anti-HIV-1 drug. The anti-DFS70 autoantibodies could be an interesting therapeutic target for anti-HIV-1 treatment. Currently, there are no studies that measured the levels of anti-DFS70 autoantibodies in HIV-1-infected individuals. SUMMARY: The anti-DFS70 antibodies bind to the DFS70 autoantigen in the same region as the HIV-IN. This fact makes the autoantibodies a potential treatment for HIV-1-infected individuals. Blood levels of anti-DFS70 antibodies have not been measured in HIV-1-infected individuals. This issue opens new lines of research about the protective role of antibodies against HIV-1 infection.


Asunto(s)
Autoanticuerpos/inmunología , Infecciones por VIH/inmunología , VIH-1 , Autoantígenos/inmunología , Infecciones por VIH/tratamiento farmacológico , Humanos
16.
Rheumatology (Oxford) ; 57(7): 1293-1298, 2018 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-29618128

RESUMEN

OBJECTIVE: The main objective was to determine the prevalence of anti-dense fine speckled (DFS70) antibodies in a stable population of undifferentiated connective tissue disease (UCTD) to better define their potential role. METHODS: Immunological and clinical records of 91 long-standing UCTD patients were studied. DFS pattern was determined using the IIF ANA test on HEp-2 cells and anti-DFS70 antibodies were tested by chemiluminescence assay and by DFS70 line immunoassay. RESULTS: Twelve (13.2%) of 91 serum samples were positive for anti-DFS70 antibodies by chemiluminescence assay and line immunoassay. There was no statistical significance between the prevalence of anti-ENA and anti-DNA autoantibodies in patients with and without anti-DFS70 antibodies. No differences were found in the clinical characteristics of both groups. The presence of the anti-DFS70 antibodies was related to the younger age class. CONCLUSION: The high prevalence of anti-DFS70 antibodies in the UCTD patients suggested the potential role of these autoantibodies as a marker in the evolution of UCTD to CTD.

17.
Phys Rev Lett ; 121(22): 226101, 2018 Nov 30.
Artículo en Inglés | MEDLINE | ID: mdl-30547655

RESUMEN

By atom manipulation we performed on-surface chemical reactions of a single molecule on a multilayer insulating film using noncontact atomic force microscopy. The single-electron sensitivity of atomic force microscopy allows us to follow the addition of single electrons to the molecule and the investigation of the reaction products. By performing a novel strategy based on long-lived doubly charged states a single molecule is fragmented. The fragmentation can be reverted by again changing the charge state of the system, characterizing a reversible reaction. The experimental results in addition to density-functional theory provide insight into the charge states of the different products and reaction pathways. Similar molecular systems could be used as charge-transfer units and to induce reversible chemical reactions.

18.
Chemistry ; 24(67): 17697-17700, 2018 Dec 03.
Artículo en Inglés | MEDLINE | ID: mdl-30324668

RESUMEN

The synthesis of a threefold symmetric nanographene with 19 cata-fused benzene rings distributed within six branches is reported. This flat dendritic starphene, which is the largest unsubstituted cata-condensed PAH that has been obtained to date, was prepared in solution by means of a palladium-catalyzed aryne cyclotrimerization reaction and it was characterized on surface by scanning probe microscopy with atomic resolution.

19.
Clin Exp Rheumatol ; 36(1): 121-126, 2018.
Artículo en Inglés | MEDLINE | ID: mdl-28770702

RESUMEN

OBJECTIVES: Autoantibodies to the dense fine speckled 70 (DFS70) antigen are common among antinuclear antibodies (ANA) positive healthy individuals (HI). We assessed the prevalence of anti-DFS70 antibodies in patients with and without ANA-associated rheumatic diseases (AARDs) by two methods: chemiluminescent immunoassay (CIA) and an indirect immunofluorescence (IIF) assay based on immunoadsorption for DFS70. METHODS: Fifty-one ANA-positive sera samples from patients with confirmed clinical diagnosis of AARD, 92 samples from HI and 85 samples submitted to a reference laboratory for routine ANA testing were evaluated for the presence of anti-DFS70 antibodies. The samples were evaluated by QUANTA Flash DFS70 CIA using BIO-FLASH instrument and by NOVA Lite selected HEp-2 kit on NOVA View - an automated IIF system. Sera with DFS positive pattern were pre-absorbed with highly purified human DFS70 antigen, and then tested again. RESULTS: Twenty-four samples (10.5%) tested by QUANTA Flash DFS70 CIA were positive for anti-DFS70 antibodies. The prevalence of monospecific anti-DFS70 antibodies was significantly higher in healthy subjects than in patients with AARDs (10.9% vs. 1.9%, p=0.02). The frequency of anti-DFS70 antibodies in samples submitted for routine ANA testing was 15.2%. A very good agreement was found between CIA and the DFS pattern identified by the automated HEp-2 IIF (kappa=0.97). In 80% of the samples obtained from patients without AARDs, immunoadsorption effectively inhibited the anti-DFS70 antibodies. CONCLUSIONS: The data confirm that mono-specific anti-DFS70 antibodies are a strong discriminator between ANA positive HI and AARD patients, and their evaluation should be included in ANA testing algorithms.


Asunto(s)
Proteínas Adaptadoras Transductoras de Señales/inmunología , Anticuerpos Antinucleares/sangre , Autoinmunidad , Enfermedades Reumáticas/inmunología , Factores de Transcripción/inmunología , Biomarcadores/sangre , Estudios de Casos y Controles , Técnica del Anticuerpo Fluorescente Indirecta , Humanos , Inmunoensayo , Técnicas de Inmunoadsorción , Mediciones Luminiscentes , Valor Predictivo de las Pruebas , Reproducibilidad de los Resultados , Enfermedades Reumáticas/sangre , Enfermedades Reumáticas/diagnóstico , Enfermedades Reumáticas/epidemiología , Estudios Seroepidemiológicos
20.
Phys Chem Chem Phys ; 20(16): 11037-11046, 2018 Apr 25.
Artículo en Inglés | MEDLINE | ID: mdl-29648564

RESUMEN

Understanding the mechanisms involved in the covalent attachment of organic molecules to surfaces is a major challenge for nanotechnology and surface science. On the basis of classical organic chemistry mechanistic considerations, key issues such as selectivity and reactivity of the organic adsorbates could be rationalized and exploited for the design of molecular-scale circuits and devices. Here we use tris(benzocyclobutadieno)triphenylene, a singular Y-shaped hydrocarbon containing antiaromatic cyclobutadienoid rings, as a molecular probe to study the reaction of polycyclic conjugated molecules with atomic scale moieties, dangling-bond (DB) dimers on a hydrogen-passivated Ge(001):H surface. By combining molecular design, synthesis, scanning tunneling microscopy and spectroscopy (STM/STS) and computational modeling, we show that the attachment involves a concerted [4+2] cycloaddition reaction that is completely site-selective and fully reversible. This selectivity, governed by the bond alternation induced by the presence of the cyclobutadienoid rings, allows for the control of the orientation of the molecules with respect to the surface DB-patterning. We also demonstrate that by judicious modification of the electronic levels of the polycyclic benzenoid through substituents, the reaction barrier height can be modified. Finally, we show that after deliberate tip-induced covalent bond cleavage, adsorbed molecules can be used to fine tune the electronic states of the DB dimer. This power to engineer deliberately the bonding configuration and electronic properties opens new perspectives for creating prototypical nanoscale circuitry.

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