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The synthesis of a [60]fullerene-benzyne building block and its further chemical cycloaddition reaction with graphene has resulted in a new all-carbon hybrid material which has been characterized by TGA, FTIR and Raman spectroscopies, XPS as well as AFM and TEM. Based on computational studies, the formation of both [2+2] and [4+2] cycloadducts on the graphene surface is feasible. [ABSTRACT FROM AUTHOR]

Cordia alliodora (coffee-shading walnut) is a species of economic importance to Colombia because of its multiple uses for farmers and for reforestation as a timber and industrial resources, mainly in the central coffee region of the country. The aim of this research was to study parameters of C. alliodora shoot and root system architecture over the first year of development. Plants were established in Pacho municipality (Cundinamarca) at an 2,150 m a.s.l. A split plot design with a randomized complete block and three replicates was applied. Within the main plot, we evaluated the substrates (soil, husk and compost 2:1:1; soil and husk 3:2; soil and husk 3:1), and withing the subplot, the mycorrhizal fungus (without fungus, Kuklospora colombiana, Glomus manihotis and Acaulospora lacunosa). Substrate type affected C. alliodora root and shoot architectural parameters. Plants transplanted into soil, husk and compost 2:1:1 had the best responses in architectural parameters: diameter of the base of the root (7.82 mm), number of secondary roots (48.4), root dry weight (5.38 g), number of leaves (47.33), dry weight of shoots (7.71 g), shoot length (72.64 g) and leaf dry weight (6.28 g) at 384 days after transplant. Since no fertilizer was applied to coffee-shading walnut plants, we conclude that the mycorrhizal fungi facilitated a better use and development of mineral elements present in the substrates.

Este trabajo fue realizado durante la estaciónde crecimiento de abril a octubre del año 2000, endos localidades: Centro Agropecuario Marengo (Mosquera)y Estación Experimental San Jorge (Soacha) enel departamento de Cundinamarca. El objetivo fueevaluar las respuestas de crecimiento y desarrollo enplantas de papa de la variedad Parda pastusa expuestasa densidades de población de: 50.000, 125.000,200.000, 275.000 y 350.000 tallos por hectárea. El incrementoen las densidades de siembra afectó la longitudtotal por planta, presentándose la mayor altura enla localidad Marengo. El área foliar se determinó comoun carácter plástico bajo las condiciones del ensayo. Eldesarrollo de las ramas o tallos secundarios tambiénfue influido por la densidad en las dos localidades. EnMarengo las plantas presentaron hábito de crecimientodecumbente, mientras en la localidad San Jorgelas plantas crecieron erectas. En general, la variedadParda pastusa presenta caracteres morfológicos que secomportaron de manera plástica, modificando el fenotipobajo las condiciones del estudio.

Purpose: HER2-targeted therapies have dramatically improved outcomes of patients with HER2-positive breast cancer (BC), as demonstrated in neoadjuvant trials. This study aims to provide real-world evidence on the use and effectiveness of combined pertuzumab, trastuzumab and chemotherapy (CT) in early-stage HER2-positive BC., Methods: A retrospective, multicentre study was conducted on patients diagnosed with HER2-positive early BC treated with neoadjuvant pertuzumab and trastuzumab plus CT at 13 Spanish sites. The primary endpoint was pathological complete response (pCR)., Results: A total of 310 patients were included. Pertuzumab and trastuzumab were combined with anthracyclines and taxanes, carboplatin and docetaxel, and taxane-based CT in 77.1%, 16.5%, and 6.5% of patients, respectively. Overall, the pCR rate was 62.2%. The pCR was higher amongst patients with hormone receptor-negative tumours and with tumours expressing higher levels of Ki-67 (> 20%). After postoperative adjuvant treatment, 13.9% of patients relapsed. Those patients who did not achieve pCR, with tumours at advanced stages (III), and with node-positive disease were more likely to experience distant relapse. Median overall survival (OS) and distant disease-free survival (D-DFS) were not reached at the study end. The estimated mean OS and D-DFS times were 7.5 (95% CI 7.3-7.7) and 7.3 (95% CI 7.1-7.5) years, respectively (both were significantly longer amongst patients who achieved pCR). Grade 3-4 anti-HER2 related toxicities were reported in six (1.9%) patients., Conclusion: Neoadjuvant pertuzumab and trastuzumab plus CT achieve high pCR rates in real-life patients with HER2-positive early BC, showing an acceptable safety profile. Innovative adjuvant strategies are essential in patients at high risk of distant disease recurrence., (© 2024. The Author(s).)

Background and Objective: Reproductive history influences breast cancer risk. We analysed its association with tumour subtype and survival in premenopausal women., Patients and Methods: Retrospective, observational study of premenopausal women with stage I-III breast carcinoma in the last 20 years. Review of reproductive history, clinical data, and treatments in health records., Results: In 661 premenopausal women (32.40% of 1377 total cases), median age was 47 years (19-53), menarche 12 (7-17), first delivery 28 (16-41) and number of deliveries 2 (0-9). One hundred and eleven (18.20%) were nulliparous. Three hundred and fifty-nine (58.80%) used natural lactation, with a median duration of 6 months. Anovulatory drugs were used by 271 (44.40%), with a median duration of 36 months. Associations were found between menarche <10 years and lower risk of luminal subtype (OR: 0.52, 95% CI: 0.28-0.94; P=.03), between menarche >11 years and lower risk of HER2 subtype (OR: 0.50, 95% CI: 0.26-0.97; P=.04) and between first birth >30 years and lower risk of triple negative subtype (OR: 0.40, 95% CI: 0.17-0.93; P=.03). The 20-year overall and disease-free survival probabilities were 0.80 (95% CI: 0.71-0.90) and 0.72 (95% CI: 0.64-0.79) respectively. Patients with ≥1 delivery had better overall survival than nulliparous patients (HR: 0.51, 95% CI: 0.27-0.96, P=.04)., Conclusions: The findings suggest an association between age at menarche and age at first delivery and breast cancer subtype. Nulliparity is associated with worse survival., (Copyright © 2023 Elsevier España, S.L.U. All rights reserved.)

Background: Implementing mammogram screening means that clinicians are seeing many breast cancers that will never develop metastases. The purpose of this study was to identify subgroups of breast cancer patients who did not present events related to long-term breast cancer mortality, taking into account diagnosis at breast screening, absence of palpability and axillary involvement, and genomic analysis with PAM50., Patients and Methods: To identify them, a retrospective observational study was carried out selecting patients without any palpable tumor and without axillary involvement, and a genomic analysis was performed with PAM50., Results: The probability of distant metastasis-free interval (DMFI) of 337 patients was 0.92 (95% CI, 0.90-0.93) at 20 years and 0.96 (95% CI, 0.92-1.00) in 95 patients (28%) with available PAM50 tests. In 22 (23.15%) luminal A tumors and in 9 (9.47%) luminal B tumors smaller than 1 cm, and in HER2 and basal type tumors, there were no metastatic events (20-year DMFI of 1.00)., Conclusion: Patients with nonpalpable breast cancer found at screening with negative nodes are at very low risk. It is possible to identify subgroups without metastatic events by determining the intrinsic subtype and tumor size less than 1 cm. Therefore, de-escalation of treatment should be considered.

The covalent incorporation of C 60 and C 70 derivatives of the well-known n-type organic semiconductor PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) onto carbon dots (CD) is described. Morphological and structural characterization reveal combined features of both pristine starting materials (CD and PCBM). Electrochemical investigations evidenced the existence of additional reduction processes to that of CD or PCBM precursors, showing rich electron-acceptor capabilities, with multistep processes in an affordable and narrow electrochemical window (ca. 1.5 V). Electronic communication in the obtained nanoconjugated species were derived from steady-state absorption and emission spectroscopies, which showed bathochromically shifted absorptions and emissions well entering the red region. Finally, the lower fluorescence quantum yield of CD-PCBM nanoconjugates, compared with CD, and the fast decay of the observed emission of CD, support the existence of an electronic communication between both CD and PCBM units in the excited state., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The thermoelectric properties of molecular junctions consisting of a metal Pt electrode contacting [60]fullerene derivatives covalently bound to a graphene electrode have been studied by using a conducting-probe atomic force microscope (c-AFM). The [60]fullerene derivatives are covalently linked to the graphene via two meta -connected phenyl rings, two para -connected phenyl rings, or a single phenyl ring. We find that the magnitude of the Seebeck coefficient is up to nine times larger than that of Au-C 60 -Pt molecular junctions. Moreover, the sign of the thermopower can be either positive or negative depending on the details of the binding geometry and on the local value of the Fermi energy. Our results demonstrate the potential of using graphene electrodes for controlling and enhancing the thermoelectric properties of molecular junctions and confirm the outstanding performance of [60]fullerene derivatives.

Safety assessment of carbon nanomaterials is of paramount importance since they are on the frontline for applications in sensing, bioimaging and drug delivery. The biocompatibility and safety of functionalized nanodiamonds (NDs) are here addressed through the study of the pro-inflammatory response of RAW-264.7 macrophages exposed to new nanodiamonds@corrole hybrids. The corrole unit selected is as a prototype for a hydrophobic organic molecule that can function as a NIR fluorophore reporter, an optical sensor, a photodynamic therapy agent or a photocatalyst. The new functional nanohybrids containing detonated nanodiamonds (NDs) were obtained through esterification using carboxylated NDs and glycol corroles. The success of the covalent functionalization via carbodiimide activation was confirmed through X-ray photoelectron spectroscopy (XPS), Raman and Fourier transform infrared (FTIR) spectroscopy. The UV-vis absorption and emission spectra of the hybrids are additive with respect to the corrole features. The cellular uptake, localization, cell viability and effects on immune cell activation of the new hybrids and of the precursors were carefully investigated using RAW-264.7 macrophages. Overall results showed that the ND@corrole hybrids had no pro-inflammatory effects on the RAW-264.7 macrophage cell line, making them an ideal candidate for a wide range of biomedical applications.

Background and Objective: To identify subgroups with good progress over an extended period, we used diagnostic screening, tumour palpability, tumour phenotype, and node involvement., Patients and Methods: We identified patients with good progress by means of a descriptive, observational and retrospective study., Results: Of 746 patients diagnosed with node-negative breast cancer between 2001 and 2015: 110 (14.75%) had non-palpable screening-diagnosed tumours; 88 (80%) were endocrine-sensitive, 10 (9.10%) were triple-negative and 11 (10%) were HER2. Only 3 patients developed metastases, and there were 4 deaths: 2 from breast cancer and 2 from other causes. The distant recurrence-free interval (DRFI) was 95.60%: 100% in 34 endocrine-sensitive histological grade 1 (equivalent to luminal A) tumours, and 94.40% (95% CI 86.76-102.04) in 54 grade 2-3 (luminal B) tumours. In triple-negative and HER2 cases, it was 100%. In tumours <1 cm it was 100%, and >1 cm it was 95.50% (95% CI 79.42-100.98)., Conclusions: Patients with non-palpable tumours detected by mammogram screening have ultralow risk. The good progress in the luminal A, triple-negative, HER2, and less than 1 cm subgroups may explain the efficacy of the treatment but it also makes them candidates to de-escalation of their treatment., (Copyright © 2022 Elsevier España, S.L.U. All rights reserved.)

The construction of supramolecular assemblies of heterogeneous materials at the nanoscale is an open challenge in science. Herein, new chiral graphene quantum dots (GQDs) prepared by amidation reaction introducing chiral amide groups and pyrene moieties into the periphery of GQDs are described. The analytical and spectroscopic data show an efficient chemical functionalization and the morphological study of the supramolecular ensembles using SEM and AFM microscopies reveals the presence of highly ordered fibers of several micrometers length. Fluorescence studies, using emission spectroscopy and confocal microscopy, reveal that the fibers stem from the π-π stacking of both pyrenes and GQDs, together with the hydrogen bonding interactions of the amide groups. Circular dichroism analysis supports the chiral nature of the supramolecular aggregates., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The increase in events associated with drought constraints plant growth and crop performance. Cacao ( Theobroma cacao L.) is sensitive to water deficit stress (DS), which limits productivity. The aim of this research was to characterise the response of seven (CCN51, FEAR5, ICS1, ICS60, ICS95, EET8, and TSH565) commercially important cacao clones to severe and temporal water deficit stress. Ten-month-old cacao trees were submitted to two treatments: well-watered and water-stressed until the leaf water potential ( Ψ leaf ) reached values between -3.0 and -3.5 MPa. The effects of hydric stress on water relations, gas exchange, photochemical activity, membrane integrity and oxidative stress-related gene expression were evaluated. All clones showed decreases in Ψ leaf , but TSH565 had a higher capacity to maintain water homeostasis in leaves. An initial response phase consisted of stomatal closure, a general mechanism to limit water loss: as a consequence, the photosynthetic rate dropped by approximately 98% on average. In some clones, the photosynthetic rate reached negative values at the maximum stress level, evidencing photorespiration and was confirmed by increased intracellular CO 2 . A second and photosynthetically limited phase was characterized by a drop in PSII quantum efficiency, which affected all clones. On average, all clones were able to recover after 4 days of rewatering. Water deficit triggered oxidative stress at the early phase, as evidenced by the upregulation of oxidative stress markers and genes encoding ROS scavenging enzymes. The effects of water deficit stress on energy metabolism were deduced given the upregulation of fermentative enzyme-coding genes. Altogether, our results suggest that the EET8 clone was the highest performing under water deficit while the ICS-60 clone was more susceptible to water stress. Importantly, the activation of the antioxidant system and PSII repair mechanism seem to play key roles in the observed differences in tolerance to water deficit stress among clones., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Osorio Zambrano, Castillo, Rodríguez Pérez and Terán.)

Carbon nanodots (CNDs) undergo electron transfer in different scenarios. Previous studies have mainly focused on the electron-accepting features of CNDs in covalently linked donor-acceptor nanoconjugates. In view of this, we decided to carry out in this study the formation of covalently linked nanoconjugates that feature electron-donating pressure synthesized carbon nanodots ( pCNDs ) and electron-accepting 11,11,12,12-tetracyano-9,10-anthra- p -quinodimethane ( TCAQ ): pCND-TCAQ . The stability of the one-electron reduced form of TCAQ renders it the acceptor of choice. Detailed structural and electrochemical investigations allowed the characterization of pCND-TCAQ . Furthermore, investigations regarding intramolecular interactions, by means of steady-state and pump-probe transient absorption spectroscopies, allowed detection and characterization of three excited state species, in general, and the pCND •+ -TCAQ •- charge-separated state, in particular.

A series of molecular precursors, containing one ( 1 and 3 ) or three ( 2 and 4 ) pyrene anchors, covalently linked to porphyrins (free base or Zn), were prepared and characterized. All of them enable their π-π stacking onto low-dimensional nanocarbons including single-walled carbon nanotubes (SWCNTs) and nanographene (NG), their individualization, and their characterization. Microscopic (TEM, AFM) and spectroscopic (steady-state UV-vis and fluorescence, spectroelectrochemistry, and transient absorption measurements) techniques were at the forefront of the characterizations and were complemented by Raman spectroscopy and theoretical calculations. Of great importance is the Raman analysis, which corroborated n-doping of the nanocarbons due to the interactions with 1 - 4 when probed in the solid state. In solution, the situation is, however, quite different. Efficient charge separation was only observed for the graphene-based system NG/ 3 .

Background: The most important decision after diagnosing terminal cancer is whether to provide active therapy or withhold treatment. Objective: To analyze the aggressiveness of care by evaluating systemic anticancer therapy (SACT) given near to death, describing this care and identifying factors that determine its use. Design: This involves retrospective observational cohorts study. Setting/Subjects: This involves patients with metastatic tumors who died at a University Hospital in Spain between 2015 and 2016. Measurements: Data obtained from prescribing oncologists and patients' clinical records, type of cancer, and information on treatment. The dependent variable used was the interval between the date of the last dose and date of death. Results: Ninety-four (32.60%) of 288 patients received SACT in the last month of life. This cohort had a higher frequency of lung cancer (OR: 1.58; CI 95%: 1.14-2.18), received more care from oncologist 2 (OR: 1.50; CI 95%: 1.08-2.08), had fewer last-line treatment cycles (OR: 1.28; CI 95%: 1.13-1.45), a lower subjective response (OR: 3.13; CI 95%: 1.34-7.29), less clinical benefit (OR: 2.38; CI 95%: 1.04-5.55), more visits to the Emergency Department (OR: 1.59; CI 95%: 1.06-2.38), and less care from the Palliative Care Unit (OR: 4.55; CI 95%: 2.69-7.70). In multivariate analysis, the predictors of having received SACT close to death remained: receiving fewer cycles of treatment (OR: 1.28; CI 95%: 1.12-1.47) and less palliative care (OR: 4.54; CI 95%: 2.56-7.69). Conclusions: A third of cancer patients received SACT in the last month of life with less efficacy and poorer quality of care than patients not receiving it.

Induced π acidity from polarizability is emerging as the most effective way to stabilize anionic transition states on aromatic π surfaces, that is, anion-π catalysis. To access extreme polarizability, we propose a shift from homogeneous toward heterogeneous anion-π catalysis on higher carbon allotropes. According to benchmark enolate addition chemistry, multi-walled carbon nanotubes equipped with tertiary amine bases outperform single-walled carbon nanotubes. This is consistent with the polarizability of the former not only along but also between the tubes. Inactivation by π-basic aromatics and saturation with increasing catalyst concentration support that catalysis occurs on the π surface of the tubes. Increasing rate and selectivity of existing anion-π catalysts on the surface of unmodified nanotubes is consistent with transition-state stabilization by electron sharing into the tubes, i.e., induced anion-π interactions. On pristine tubes, anion-π catalysis is realized by non-covalent interfacing with π-basic pyrenes., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

After the last epidemic of the Zika virus (ZIKV) in Brazil that peaked in 2016, growing evidence has been demonstrated of the link between this teratogenic flavivirus and microcephaly cases. However, no vaccine or antiviral drug has been approved yet. ZIKV and Dengue viruses (DENV) entry to the host cell takes place through several receptors, including dendritic cell-specific intercellular adhesion molecule-3-grabbing nonintegrin (DC-SIGN), so that the blockade of this receptor through multivalent glycoconjugates supposes a promising biological target to inhibit the infection process. In order to get enhanced multivalency in biocompatible systems, tridecafullerenes appended with up to 360 1,2-mannobiosides have been synthesized using a strain-promoted cycloaddition of azides to alkynes (SPAAC) strategy. These systems have been tested against ZIKV and DENV infection, showing an outstanding activity in the picomolar range.

Fullerene receptors prepared by a twofold Cu I -catalyzed azide-alkyne cycloaddition reaction with π-extended tetrathiafulvalene (exTTF) have been covalently linked to single-walled carbon nanotubes and multi-walled carbon nanotubes. The nanoconjugates obtained were characterized by several analytical, spectroscopic and microscopic techniques (TEM, FTIR, Raman, TGA and XPS), and evaluated as C 60 receptors by using UV-Vis spectroscopy. The complexation between the exTTF-triazole receptor in the free state and C 60 was also studied by UV-Vis and 1 H NMR titrations, and compared with analogous triazole-based tweezer-type receptors containing the electron-acceptor 11,11,12,12-tetracyano-9,10-anthraquinodimethane and benzene rings instead of exTTF motifs, providing in all cases very similar values for the association constant (log K a ≈3.0-3.1). Theoretical density functional theory calculations demonstrated that the enhanced interaction between the host and the guest upon increasing the size of the π-conjugated arms of the tweezer is compensated by an increase in the energy penalty needed to distort the geometry of the host to wrap C 60 ., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Water-soluble fluorescent graphene quantum dots have been successfully prepared through a top-down approach, that is, starting with graphite, and covalently functionalizing it with π-extended tetrathiafulvalene. Charge transfer investigations reveal noticeably slower charge recombination when compared with exTTF nanoconjugates featuring carbon nanodots, for which a larger presence of trap states is observed.

Background and Objectives: In endocrine-sensitive, HER-2 negative, node negative breast cancer, the presence of a low genomic risk allows treatment with adjuvant endocrine therapy alone, obtaining excellent survival rates. The justification for this study is to show that excellent survival rates are also obtained by treating with adjuvant hormone therapy alone, based on clinical risk assessment., Patients and Methods: A descriptive, observational and retrospective study was performed between 2006 and 2016 with endocrine-sensitive, HER-2 negative, node negative breast cancer, greater than 1cm or between 0.6 and 1cm with unfavourable features. Retrospective review of health records. Mortality data of the National Registry of Deaths., Results: A total of 203 patients were evaluable for survival. One hundred and twenty-three (60.50%) were treated with adjuvant endocrine therapy alone, 77 (37.90%) with chemotherapy and endocrine therapy, one (0.50%) with chemotherapy alone and 2 (1%) were not treated. The overall survival rate at 5 years was 97% (95% confidence interval [CI] 94-100). Distant recurrence-free interval was 94% (95% CI 90-98). In the subgroup of patients treated with endocrine therapy alone, overall survival and distant recurrence-free interval rates at 5 years were 98% (95% CI 95-100) and 97% (95% CI 93-100), respectively., Conclusions: Patients with endocrine-sensitive, HER-2-negative, node negative breast cancer treated with endocrine therapy alone according to their clinical risk have similar survival outcomes as those treated with endocrine therapy according to their genomic risk., (Copyright © 2018 Elsevier España, S.L.U. All rights reserved.)

SWCNTs, MWCNTs, and SWCNHs have been employed as virus-mimicking nanocarbon platforms for the multivalent presentation of carbohydrates in an artificial Ebola virus infection model assay. These carbon nanoforms have been chemically modified by the covalent attachment of glycodendrons and glycofullerenes using the CuAAC "click chemistry" approach. This modification dramatically increases the water solubility of these structurally different nanocarbons. Their efficiency in blocking DC-SIGN-mediated viral infection by an artificial Ebola virus has been tested in a cellular experimental assay, finding that glycoconjugates based on MWCNTs functionalized with glycofullerenes are potent inhibitors of viral infection.

Carbon nanodots (CNDs) were synthesized using low-cost and biocompatible starting materials such as citric acid/urea, under microwave irradiation, and constant pressure conditions. The obtained pressure-synthesized CNDs (pCNDs) were covalently modified with photo- and electroactive π-extended tetrathiafulvalene (exTTF) by means of a two-step esterification reaction, affording pCND-exTTF. The electronic interactions between the pCNDs and exTTF were investigated in the ground and excited states. Ultrafast pump-probe experiments assisted in corroborating that charge separation governs the deactivation of photoexcited pCND-exTTF. These size-regular structures, as revealed by AFM, are stable electron donor-acceptor conjugates of interest for a better understanding of basic processes such as artificial photosynthesis, catalysis, and photovoltaics, involving readily available fluorescent nanodots., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Near-infrared (NIR) absorbing nanomaterials, built from anionic heptamethine cyanine dyes and single-walled carbon nanotubes or few-layer graphene, are presented. The covalent linkage, using 1,3-dipolar cycloaddition reactions, results in nanoconjugates that synchronize the properties of both materials, as demonstrated by an in-depth characterization study carried out by transmission electron microscopy, atomic force microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. UV-vis-NIR and Raman spectroscopies further confirmed the unique electronic structure of the novel photoactive nanomaterials., Competing Interests: The authors declare no competing financial interest.

Graphene nanobuds were prepared via the non-covalent anchoring of C 60 -based molecules endowed with one or three pyrene units, respectively. TGA, FTIR, UV-Vis and TEM investigations confirmed the formation of nanohybrids. For the two molecular derivatives, striking differences were determined in their interaction with graphene or carbon surfaces by Raman, cyclic voltammetry and molecular mechanics calculations, revealing the important role of pyrene adsorption in modulating the electronic properties of the nanohybrids.

New supramolecular (metal)porphyrin/SWCNT hybrids have been synthesized through a combination of hydrogen bond and electrostatic interactions. Our experimental findings reveal through different techniques (XPS, TGA, UV-vis, Raman, and TEM) an efficient n-doping of the SWCNT from the electron donor (metal)porphyrin through the efficient and strong amidinium-carboxylate connectivity.

Graphene-based materials (GBMs), with graphene, their most known member, at the head, constitute a large family of materials which has aroused the interest of scientists working in different research fields such as chemistry, physics, or materials science, to mention a few, arguably as no other material before. In this review, we offer a general overview on the most relevant synthetic approaches for the covalent and non-covalent functionalization and characterization of GBMs. Moreover, some representative examples of the incorporation into GBMs of electroactive units such as porphyrins, phthalocyanines, or ferrocene, among others, affording electron donor-acceptor (D-A) hybrids are presented. For the latter systems, the photophysical characterization of their ground- and excited-state features has also been included, paying particular attention to elucidate the fundamental dynamics of the energy transfer and charge separation processes of these hybrids. For some of the presented architectures, their application in solar energy conversion schemes and energy production has been also discussed.

Objective: The use of antineoplastic medicines in special situations is common in clinical practice; it is strongly regulated and there is little information on its outcomes. We have analysed such use and health outcomes., Methods: All off-label cases between 2005 and 2015, with any type of cancer and in any stage were included. Health histories of a single health centre were reviewed to gather information on treatment features, response, survival, andtoxicity., Results: 85 men and 83 women, aged 56, had largely metastatic tumours treated with a median of 4 cycles (0-118) of chemotherapy, hormone therapy, or biotherapy, for palliative purposes between 1st and 4th lines (80% of cases). The subjective response rate was 32.5%, complete objective 1.9%, partial 8.8%, stabilisation 15.6%, progression 38.8%, and not assessable 35.1%. The median duration of response was 2.5 months (1-17), progression-free survival (PFS) 5 months (4 - 21.3), and overall survival (OS) 11 months (9.2-20.6). In the univariate analysis, performance status, treatment line, number of cycles, and type of response influenced on OS. In the multivariate model, the functional status (HR 0.36; CI 95% 0.17-0.77. P= 0.009) and number of cycles (HR 3.66; CI 95% 2.08-6.44. P= 0.0001) influenced independently on overall survival. The most frequent grade 3 and 4 toxicity were asthenia (19%), neutropenia (10.7%), and nausea and vomiting (8.9%)., Conclusions: Off-label antineoplastic drugs were mostly used in metastatic tumours, with little effectiveness. The functional status must be considered to select the patients to be treated., (Copyright AULA MEDICA EDICIONES 2017. Published by AULA MEDICA. All rights reserved.)

The use of multivalent carbohydrate compounds to block cell-surface lectin receptors is a promising strategy to inhibit the entry of pathogens into cells and could lead to the discovery of novel antiviral agents. One of the main problems with this approach, however, is that it is difficult to make compounds of an adequate size and multivalency to mimic natural systems such as viruses. Hexakis adducts of [60]fullerene are useful building blocks in this regard because they maintain a globular shape at the same time as allowing control over the size and multivalency. Here we report water-soluble tridecafullerenes decorated with 120 peripheral carbohydrate subunits, so-called 'superballs', that can be synthesized efficiently from hexakis adducts of [60]fullerene in one step by using copper-catalysed azide–alkyne cycloaddition click chemistry. Infection assays show that these superballs are potent inhibitors of cell infection by an artificial Ebola virus with half-maximum inhibitory concentrations in the subnanomolar range.

The reactivity of several carbon nanoforms (CNFs), single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs) and graphene, has been investigated through a combination of arylation and click chemistry Cu(I)-mediated azide-alkyne cycloaddition (CuAAC) reactions. The approach is based on the incorporation of electroactive π-extended tetrathiafulvalene (exTTF) units into the triazole linkers to modulate the electronic properties of the obtained conjugates. The introduction of strain, by bending the planar graphene sheet into a 3D carbon framework, is responsible for the singular reactivity observed in carbon nanotubes. The formed nanoconjugates were fully characterized by analytical, spectroscopic, and microscopic techniques (TGA, FTIR, Raman, UV-Vis-NIR, cyclic voltammetry, TEM and XPS). In the case of SWCNT conjugates, where the functionalization degree is higher, a series of steady-state and time resolved spectroscopy experiments revealed a photoinduced electron transfer from the exTTF unit to the electron-accepting SWCNT.

A complementary double-covalent functionalization of single-wall carbon nanotubes (SWCNTs) that involves both solubilizing ionic liquids and electroactive moieties is reported. Our strategy is a simple and efficient methodology based on the stepwise functionalization of the nanotube surface with two different organic moieties. In a first instance, oxidized SWCNTs are amidated with ionic liquid precursors, and further treated with n-butyl bromide to afford SWCNTs functionalized with 1-butylimidazolium bromide. This approach allows tuneable polarity induced by anion exchange, which has an effect on the relative solubility of the modified SWCNTs in water. Subsequently, a 1,3-dipolar cycloaddition reaction was performed to introduce the electron-acceptor 11,11,12,12-tetracyano-9,10-anthra-para-quinodimethane (TCAQ) unit on the SWCNTs. Furthermore, to evaluate the influence of the functional group position, the TCAQ electroactive molecule was anchored through an esterification reaction onto previously oxidized SWCNTs, followed by the Tour reaction to introduce the ionic liquid functions. IR and Raman spectroscopies, thermogravimetric analysis (TGA), UV/Vis/NIR spectroscopy, transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) were employed and clearly confirmed the double-covalent functionalization of the SWCNTs., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Introduction: Health care professionals are constantly seeking novel approaches to treat pressure ulcers because of the impact they have on patient quality of life and health, as well as the costs associated with treating them., Methods: A review of the literature from 2002-2012 was conducted on the clinical usefulness of hyaluronic acid in tissue regeneration. Reports suggest that the therapeutic use of hyaluronic acid favors tissue regeneration by modulating the hydration and osmotic balance., Results: Different studies show that hyaluronan and derived-hyaluronic acid products are safe and free of adverse effects. Furthermore, a few studies examine the hyaluronic acids repercussions in pressure ulcer treatment., Conclusion: Reports suggest that this molecule could be successfully used to treat pressure ulcers in association with conventional measures.

Background and Aims: T. gondii is a causal agent of encephalitis in immunocompromised patients. Pyrimethamine (PYR) has been the treatment of choice for toxoplasmosis. The aim of this study was to analyze the effect of nitazoxanide and pyrimethamine on astrocytes infected with T. gondii in vitro., Methods: Rat astrocytes were cultured and infected with T. gondii. The effect of nitazoxanide (10, 20 and 30 μg/mL) and pyrimethamine (7, 10 and 13 μg/mL) on astrocytes infected was evaluated at 24 and 48 h post-infection. Tachyzoites and astrocytes were detected by the immunocytochemical method. T. gondii viability in astrocytes infected and treated with NTZ and PYR as well as NTZ and PYR cytotoxicity on astrocytes in vitro were evaluated by the MTT assay., Results: The number of parasites in astrocytes treated with the drugs was significantly reduced when compared to control (p <0.001) at 24 and 48 h. Nitazoxanide produced 97% T. gondii death in a concentration of 10 μg/mL in 48 h infected astrocytes. At 48 h, the death rate of T. gondii was higher when treated with nitazoxanide than with pyrimethamine. A higher toxicity rate in astrocyte was observed when using pyrimethamine at 40 μg/mL., Conclusions: Nitazoxanide reduced T. gondii infection more efficiently than pyrimethamine and is not cytotoxic to astrocytes at the administered dose., (Copyright © 2013 IMSS. Published by Elsevier Inc. All rights reserved.)

Graphene is a unique material with outstanding mechanical and electronic properties. For solution processes graphene layers have to be stabilized by means of molecular or supramolecular chemical derivatization, prior to their transfer to solid substrates. The most common chemical methodology for the preparation of graphene involves the formation of graphene oxide under highly oxidizing conditions, which even after reduction, lacks the electronic quality of pristine graphene. Presently, there is increasing concern in the chemical community about the starting material quality, and recent efforts are directed to wet chemical approaches toward high-quality graphene flakes which encompass the use of graphite as initial material. In addition, epitaxial growth of graphene on metallic surfaces is becoming a powerful technique for the production of pristine graphene with a control on its electronic properties, somehow due to the supramolecular interaction with the metallic surface. Current approaches for the preparation of modified pristine graphene are the aim of this review.

Nonsteroidal anti-inflammatory drugs (NSAIDs) are among the most widely prescribed drugs worldwide and serve as treatment of some degenerative inflammatory joint diseases. The aim of the present study was to investigate the influence of different concentrations of three NSAIDs on cell proliferation, differentiation, antigenic profile, and cell cycle in the human MG-63 osteosarcoma cell line, incubated for 24 hr. All NSAIDs had an inhibiting effect on osteoblastic proliferation. Treatments for 24 hr had small but significant effects on the antigenic profile. No treatment altered osteocalcin synthesis. Indomethacin and nimesulide treatments arrested the cell cycle at G(0)/G(1). These results suggest that indomethacin, nimesulide, and diclofenac appear to have no effects on osteocalcin synthesis and a slight effect on the antigenic profile. They may delay bone regeneration due to their inhibiting effect on osteoblast growth. Therefore, these drugs should only be used in situations that do not require rapid bone healing.

Unlabelled: Anti-inflammatories are divided between steroidal and non-steroidal drugs according to their chemical nature. They are frequently used in combination to achieve analgesia and reduce inflammation after surgery, especially when bone tissue is affected. However, their effects on bone level are not well known, and results of the scant studies in humans have been contradictory., Objective: To study the short-term effect of ibuprofen, acetaminophen and methylprednisolone at therapeutic doses on different cell parameters of human osteoblasts in culture., Design: Osteoblasts were derived from samples of human bone sections obtained during third molar surgery. Cell lines were incubated in culture medium with different concentrations of anti-inflammatories (5 or 25 μM of ibuprofen or acetaminophen, 10(-6) or 10(-8)M of methylprednisolone) for 24 or 48h. Flow cytometry was used to study proliferation, antigenic profile, phagocytic activity and cell cycle., Results: All three anti-inflammatories inhibited osteoblastic proliferation, but no significant cell cycle changes were observed. The drugs had no effect on antigenic profile or phagocytic capacity., Conclusion: These results suggest that ibuprofen, acetaminophen and methylprednisolone at therapeutic doses reduce osteoblast growth without affecting other cell parameters, such as antigenic profile or cell cycle. Use of these drugs should be reconsidered in clinical situations that require a rapid healing of bone defects., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

[BMI][PF(6)] has been supported on silica and alumina in order to study the effect of these classical oxide supports on the structure of the ionic liquid. A widespread characterization by TGA, DSC, XRD and solid NMR of thin films of [BMI][PF(6)] immobilized on these amorphous supports has evidenced a dramatic effect on the ionic liquid structure depending on the nature of the support. For the alumina composite, a loss of the supramolecular arrangement of the ionic liquid occurs, while for the analogous silica composite, ions interact strongly with the support, leading to a [BMI][PF(6)] thermostability decrease.

Background: Overweight and obesity are positively correlated with increased risk of morbidity and mortality., Aim: To evaluate whether obesity may be considered an independent cardiovascular risk factor in patients of ages from 35 to 74 years followed-up for 10 years., Design of Study: Observational, longitudinal retrospective study., Setting: Primary care practices in Badajoz (Spain)., Method: A cohort of 899 patients (mean 55.7 years; 58.2% female) without evidence of cardiovascular disease was studied., Results: A total of 33.5% of the population were obese (body mass index > or =30 kg/m2). Patients meeting the obesity criteria were more commonly female (36.6%) and were older, had higher mean values of blood pressure and triglycerides, higher percentages of diabetes, and higher coronary risk using either the original Framingham or the Framingham function calibrated for the Spanish population (Framingham-REGICOR). During the follow-up period, the rates of cardiovascular events and death in patients with obesity tended to be higher: 16.3% versus 11.7%, P = 0.056 and 4.7% versus 2.2%, P<0.05, respectively. In the final model of the logistic regression multivariate analysis, the significant predictors of cardiovascular events in patients with obesity were age, sex (male), diastolic blood pressure, diabetes, and smoking. The highest odds ratio corresponded to smoking (odds ratio 2.03; 95% confidence interval = 1.22 to 3.38)., Conclusion: Obesity may not be considered an independent cardiovascular risk factor in patients aged from 35 to 74 years followed-up for 10 years.

Highly active rhodium catalysts have been prepared by immobilization of an ionic liquid film on carbon nanotubes functionalized with imidazolium-based ionic moieties.

The principal objective of this study was to evaluate, at 2 years of age, the neurological development of a group of children who had been treated in the neonatal intensive care unit (NICU) of the National Institute of Perinatology of Mexico. All the children born between 1 January 1992 and 31 December 1993 who had entered the NICU and stayed for 3 or more days were studied from the neurological, psychological, auditory, linguistic, motor, and neuromuscular standpoint. This group included 134 patients, who had had an average gestational age of 32 weeks and an average birth-weight of 1,677 g. They had stayed in the hospital an average of 51 days, and 75% of them had undergone artificial respiration. In the examination done at age 2, 66.5% of the children were normal and 8.2% had serious impairments. There were statistically significant associations between their neurological condition and the days of artificial respiration (P < 0.0001), the days spent in the NICU (P < 0.000004), and the gestational age in weeks (P < 0.03). There was no association between the children's sex and the results of the assessments. The study results showed a decrease in neural abnormalities in comparison with the results obtained in similar studies 10 years earlier.

Subependymal/intraventricular hemorrhage (SE/IVH) is the most frequently encountered type of hemorrhage in the neonatal period. Premature infants often develop SE/IVH which remains is one of most serious neonatal events. We studied a group of 96 premature newborn infants: half of which were diagnosed with SE/IVH. We evaluated the babies at six and 12 months of age which++ a battery of neurobehavioral exams, including neurological, psychological, motor an audiological test. In 52 of infants with SE/IVH showed some type of neurobehavioral abnormality, compared with 13% of non-SE/IVH infants. In 56% of SE/IVH infants had neurological abnormalities at 12 months (P < 0.0001) difference with non-SE/IVH), predominantly in areas of muscle tone and reflex. Motor abnormalities were encountered in 42% of SE/IVH children, and in 4% of non-SE/IVH children at 12 months. Psychometric abnormalities at 12 months were noted in 53% of the SE/IVH group. Hypocusis were noted in 38% of the SE/IVH group and in 15% of the non-SE/IVH group.