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BACKGROUND: In Mexico the reports mention between 114 and 122 daily deaths associated with smoking. In 2011, Hallan and Orth published the results of a 10-year follow-up of more than 65,000 participants, concluding that the risk of developing renal failure is 3 to 4 times higher in smokers than in non-smokers. OBJECTIVE: To demonstrate how the use of tobacco in patients without comorbidities may favor glomerular hyperfiltration, thus increasing the risk of chronic kidney disease. MATERIAL AND METHOD: A cross-sectional, analytical, prospective study was conducted with patients from the Xoco General Hospital, Mexico City; they were divided into 2 groups. Blood samples were taken to obtain the serum creatinine and urea values, using the MDRD and CKD formulas. EPI estimated the glomerular filtration rate. Statistical analysis was performed with the SPSS V21 program. RESULTS: There were included 152 patients. Majority of the smoking population had high dependence with 20 cases and a prevalence of 27%. With a value of p = 0.023 for glomerular filtration rate (GFR) by MDRD and p = 0.006 for CKD-EPI. They had statistically significant differences. A statistically significant positive correlation (r = 0.413, p < 0.01) between the smoking index and the GFR measured by MDRD was demonstrated in this study. Statistically significant positive correlation (r = 0.238, p = 0.041) was also found between smoking index and GFR measured by CKD-EPI. CONCLUSION: Smoking causes high glomerular hyperfiltration compared to not-smoking subjects; this relation is dosis-dependent. [ABSTRACT FROM AUTHOR]

By reacting a 3,6-ditriazolyl-2,5-dihydroxybenzoquinone (H 2 trz 2 An) anilato linker with Ln III ions (Ln III = Dy, Tb, Ho), two different series of polymorphs, formulated as [Ln 2 (trz 2 An) 3 (H 2 O) 4 ] n ·10H 2 O (Dy III , 1a; Tb III , 2a, Ho III , 3a) and [Ln 2 (trz 2 An) 3 (H 2 O) 4 ] n ·7H 2 O (Dy III , 1b, Tb III , 2b, Ho III , 3b) have been obtained. In these series the two Dy III -coordination networks (1a and 1b) and the Tb III -coordination polymer (2b) show a Single Ion Magnet (SIM) behavior. 1-3a MOFs show reversible structural flexibility upon removal of a coordinated water molecule from a distorted hexagonal 2D framework to a distorted 3,6-brickwall rectangular 3D structure in [Ln 2 (trz 2 An) 3 (H 2 O) 2 ] n ·2H 2 O (Dy III , 1a&#95;des; Tb III , 2a&#95;des, Ho III , 3a&#95;des) involving shrinkage/expansion of the hexagonal-rectangular networks. Noteworthy, 2b represents the first example of a Tb III -anilate-based coordination polymer showing SIM behaviour to date and the best SIM properties within the polymorphs. Theoretical investigation via ab initio CASSCF calculations supports this behavior, since 2b shows less mixing between the m J states of the ground state among all the studied complexes., Competing Interests: There are no conflicts to declare., (This journal is © the Partner Organisations.)

The preparation of Fe(II) complexes combining monodentate NCX - (X = S or Se) and the tetradentate Schiff base chiral ligands RR -L 1 and SS -L 1 = ( RR - or SS -L 1 = 1 R ,2 R or 1 S ,2 S )- N 1 , N 2 -bis(pyridin-2-ylmethylen)cyclohexane-1,2-diamine in acetone results in an unexpected reaction. Thus, four enantiomerically pure compounds of formulas [Fe( RR-S -L 2 )(NCX) 2 ] and [Fe( SS-R -L 2 )(NCX) 2 ] (X = S or Se) are formed by the new asymmetrical ligand L 2 . In L 2 , one acetone solvent molecule is incorporated into the ligand forming a bond with the C atom of one of the two CN imine groups of L 1 , which is transformed into an amine (Mannich reaction). This reaction is diastereoselective as the incorporation of acetone leads to an asymmetric C adjacent to the NH group with opposite chirality S - or R - to that of the cyclohexane carbons ( RR - or SS -, respectively). Therefore, L 2 contains three C chiral centers. Structural and magnetic characterization of these compounds demonstrates that they show in the bulk a gradual spin-crossover behavior and LIESST effect. Interestingly, the presence of an intramolecular hydrogen bond between the integrated acetone molecule and the NH group can trigger a secondary stimuli-responsive behavior in the system. Therefore, by changing the solvent polarity, the color of the complex in solution can be easily tuned.

A large diversity of epigenetic factors, such as microRNAs and histones modifications, are known to be capable of regulating gene expression without altering DNA sequence itself. In particular, miR-1 is considered the first essential microRNA in cardiac development. In this study, miR-1 potential role in early cardiac chamber differentiation was analyzed through specific signaling pathways. For this, we performed in chick embryos functional experiments by means of miR-1 microinjections into the posterior cardiac precursors-of both primitive endocardial tubes-committed to sinoatrial region fates. Subsequently, embryos were subjected to whole mount in situ hybridization, immunohistochemistry and RT-qPCR analysis. As a relevant novelty, our results revealed that miR-1 increased Amhc1 , Tbx5 and Gata4 , while this microRNA diminished Mef2c and Cripto expressions during early differentiation of the cardiac sinoatrial region. Furthermore, we observed in this developmental context that miR-1 upregulated CrabpII and Rarß and downregulated CrabpI , which are three crucial factors in the retinoic acid signaling pathway. Interestingly, we also noticed that miR-1 directly interacted with Hdac4 and Calm1 / Calmodulin , as well as with Erk2 / Mapk1 , which are three key factors actively involved in Mef2c regulation. Our study shows, for the first time, a key role of miR-1 as an epigenetic regulator in the early differentiation of the cardiac sinoatrial region through orchestrating opposite actions between retinoic acid and Mef2c , fundamental to properly assign cardiac cells to their respective heart chambers. A better understanding of those molecular mechanisms modulated by miR-1 will definitely help in fields applied to therapy and cardiac regeneration and repair.

Introduction: Diffuse interstitial lung disease (ILD) describes a broad group of pulmonary inflammatory and fibrosis disorders. Asbestosis and silicosis are the main causes linked to occupational exposure. The aim of this study was to estimate the proportion of cases with possible occupational origin and describe their exposure, clinical, and occupational status., Method: We conducted a retrospective longitudinal study of ILD cases between 2017 - 2022 at the University Hospital of Navarra was conducted. Information was supplemented with interviews of cases with possible occupational origin. The occupational proportion was calculated, labor and clinical characteristics analyzed, by statistical comparison of percentages and means., Results: Out of 1067 ILD cases, 56 had a possible occupational origin 5,2% (95% CI 3,9-6,6%). 36 (64,3%) corresponded to asbestosis, 15 (26,8%) to silicosis, and 5 (8,9%) to unspecified pneumoconiosis. The most frequent activities in silicosis were "stone cutting-carving" and in asbestosis "manufacture of iron products". The average age of asbestosis cases was higher than that of silicosis cases (78,2 vs. 67,3 years), as well as their clinical manifestation. Five cases (8,9%) had been recognized as occupational diseases., Conclusions: The implementation of a computer tool in medical records has made it possible to estimate the magnitude and assess the evolution of occupational ILD treated in the Public Health Service. Economic activities reflect the economic risk structure of the region. However, there is a lack of recognition of these diseases as occupational illnesses and they represent a preventable burden of respiratory disease.

Kaempferol, a flavonoid present in many food products, has chemical and cellular antioxidant properties that are beneficial for protection against the oxidative stress caused by reactive oxygen and nitrogen species. Kaempferol administration to model experimental animals can provide extensive protection against brain damage of the striatum and proximal cortical areas induced by transient brain cerebral ischemic stroke and by 3-nitropropionic acid. This article is an updated review of the molecular and cellular mechanisms of protection by kaempferol administration against brain damage induced by these insults, integrated with an overview of the contributions of the work performed in our laboratories during the past years. Kaempferol administration at doses that prevent neurological dysfunctions inhibit the critical molecular events that underlie the initial and delayed brain damage induced by ischemic stroke and by 3-nitropropionic acid. It is highlighted that the protection afforded by kaempferol against the initial mitochondrial dysfunction can largely account for its protection against the reported delayed spreading of brain damage, which can develop from many hours to several days. This allows us to conclude that kaempferol administration can be beneficial not only in preventive treatments, but also in post-insult therapeutic treatments.

Molecular motors (MM) are molecular machines, or nanomachines, that rotate unidirectionally upon photostimulation and perform mechanical work on their environment. In the last several years, it has been shown that the photomechanical action of MM can be used to permeabilize lipid bilayers, thereby killing cancer cells and pathogenic microorganisms and controlling cell signaling. The work contributes to a growing acknowledgement that the molecular actuation characteristic of these systems is useful for various applications in biology. However, the mechanical effects of molecular motion on biological materials are difficult to disentangle from photodynamic and photothermal action, which are also present when a light-absorbing fluorophore is irradiated with light. Here, an overview of the key methods used by various research groups to distinguish the effects of photomechanical, photodynamic, and photothermal action is provided. It is anticipated that this discussion will be helpful to the community seeking to use MM to develop new and distinctive medical technologies that result from mechanical disruption of biological materials., (© 2023 Wiley-VCH GmbH.)

There is a pressing need for more precise biomarkers of chronic kidney disease (CKD). Plasma samples from 820 subjects [231 with CKD, 325 with end-stage kidney disease (ESKD) and 264 controls] were analyzed by liquid chromatography with tandem mass spectrometry (LC-MS/MS) to determine a metabolic profile of 28 amino acids (AAs) and biogenic amines to test their value as markers of CKD risk and progression. The kynurenine/tryptophan ratio showed the strongest correlation with estimated glomerular filtration rate values (coefficient = -0.731, p < 0.0001). Models created with orthogonal partial least squares-discriminant analysis (OPLS-DA) containing the metabolic signature showed a high goodness of fit and predictability for controls/CKD (R2X:0.73:R2Y:0.92:Q2:0.92, p < 0.0001) and lower values for CKD/ESKD (R2X:0.56:R2Y:0.59:Q2:0.55, p < 0.0001). Based on generated VIP scores, the most relevant markers for segregating samples into control/CKD and CKD/ESKD groups were citrulline (1.63) and tryptophan (1.47), respectively. ROC analysis showed that the addition of the metabolic profile to a model including CKD classic risk factors improved the AUC from 86.7% (83.6-89.9) to 100% (100-100) for CKD risk ( p < 0.0001) and from 63.0% (58.2-67.8) to 96.5% (95.3-97.8) for the risk of progression from CKD to ESKD ( p < 0.0001). Plasma concentrations of AAs and related amines may be useful as diagnostic biomarkers of kidney disease, both for CKD risk and for progression of CKD patients to ESKD.

Understanding the directed motion of a single molecule on surfaces is not only important in the well-established field of heterogeneous catalysis but also for the design of artificial nanoarchitectures and molecular machines. Here, we report how the tip of a scanning tunneling microscope (STM) can be used to control the translation direction of a single polar molecule. Through the interaction of the molecular dipole with the electric field of the STM junction, it was found that both translations and rotations of the molecule occur. By considering the location of the tip with respect to the axis of the dipole moment, we can deduce the order in which rotation and translation take place. While the molecule-tip interaction dominates, computational results suggest that the translation is influenced by the surface direction along which the motion takes place.

Ocular neurodegenerative diseases such as glaucoma, diabetic retinopathy, and age-related macular degeneration are common retinal diseases responsible for most of the blindness causes in the working-age and elderly populations in developed countries. Many of the current treatments used in these pathologies fail to stop or slow the progression of the disease. Therefore, other types of treatments with neuroprotective characteristics may be necessary to allow a more satisfactory management of the disease. Citicoline and coenzyme Q10 are molecules that have neuroprotective, antioxidant, and anti-inflammatory properties, and their use could have a beneficial effect in ocular neurodegenerative pathologies. This review provides a compilation, mainly from the last 10 years, of the main studies that have been published on the use of these drugs in these neurodegenerative diseases of the retina, analyzing the usefulness of these drugs in these pathologies.

Three solvatomorphs of the iron(II) complex of 2,6-di[4-(ethylcarboxy)pyrazol-1-yl]pyridine (bpCOOEt 2 p) of formulas [Fe(bpCOOEt 2 p) 2 ](ClO 4 ) 2 ·1.5MeNO 2 ( 1 ), [Fe(bpCOOEt 2 p) 2 ](ClO 4 ) 2 ·MeNO 2 ( 2 ), and [Fe(bpCOOEt 2 p) 2 ](ClO 4 ) 2 ·2MeNO 2 ( 3 ) have been prepared and characterized. They show interesting spin-crossover (SCO) properties ranging from partial to complete thermal spin transitions and a light-induced excited spin-state trapping (LIESST) effect. In solvatomorph 2 , a robust structure is formed with channels that enable the entrance or removal of solvent molecules by vapor diffusion without losing the crystallinity. Thus, solvent-exchanged samples [Fe(bpCOOEt 2 p) 2 ](ClO 4 ) 2 ·MeNO 2 ( 2·MeNO 2 ), [Fe(bpCOOEt 2 p) 2 ](ClO 4 ) 2 ·MeCN ( 2·MeCN ), [Fe(bpCOOEt 2 p) 2 ](ClO 4 ) 2 ·0.5Me 2 CO (2·Me 2 CO ), and [Fe(bpCOOEt 2 p) 2 ](ClO 4 ) 2 ·MeCOOH ( 2·MeCOOH ) were prepared by vapor diffusion of the solvents in a crystal of the compound previously heated to 400 K in a single-crystal to single-crystal (SCSC) fashion. Interestingly, this causes a change of spin state with a stabilization of the low-spin state in 2·Me 2 CO and the high-spin state in 2·MeCN . Therefore, the SCO properties of 2 can be tuned in a reversible way by exposure to different solvents., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Building nanostructures one-by-one requires precise control of single molecules over many manipulation steps. The ideal scenario for machine learning algorithms is complex, repetitive, and time-consuming. Here, we show a reinforcement learning algorithm that learns how to control a single dipolar molecule in the electric field of a scanning tunneling microscope. Using about 2250 iterations to train, the algorithm learned to manipulate the molecule toward specific positions on the surface. Simultaneously, it generates physical insights into the movement as well as orientation of the molecule, based on the position where the electric field is applied relative to the molecule. This reveals that molecular movement is strongly inhibited in some directions, and the torque is not symmetric around the dipole moment.

A bifunctionalized polyoxometalate (POM), [V 6 O 19 (C 16 H 15 N 6 O) 2 ] 2- , which contains a redox active hexavanadate moiety covalently linked to two tridentate 2,6-bis(pyrazol-1-yl)pyridine (1-bpp) ligands, has been prepared and characterized. Reaction of this hybrid molecule with Fe(ii) or Zn(ii) ions produces crystalline neutral 1D networks of formula Fe[V 6 O 19 (C 16 H 15 N 6 O) 2 ]·solv (2) and Zn[V 6 O 19 (C 16 H 15 N 6 O) 2 ]·solv (3) (solv = solvent molecules). Magnetic properties of 2 show an abrupt spin-crossover (SCO) with the temperature, which can be induced by light irradiation at 10 K (Light-Induced Excited Spin-State Trapping, LIESST effect). Interestingly, this porous and flexible structure enables reversible exchange of solvents in 2, which allows tuning the temperature of the thermal SCO. In 2 and 3, the hexavanadate unit can be reduced by electrochemical or chemical means in a reversible way. Chemical reduction and reoxidation by a postsynthetic method is accompanied by the insertion in the structure of the reductant and oxidant molecules (cobaltocene and tribromide, respectively), which provokes drastic changes in the spin state of Fe(ii). This leads to an elegant switching multifunctional material in which SCO properties of the Fe(ii) complexes coexist with the redox properties of the POM and can be tuned by a variety of stimuli such as temperature, light, solvent exchange or electron transfer. During the reduction process, 3 undergoes a single-crystal-to-single-crystal one-electron reduction, which confirms the presence of cobaltocenium cations by single crystal X-ray diffraction., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

An understanding of the rotary cycle of molecular motors (MMs), a key component of an approach to opening cells using mechanical motion, is important in furthering the research. Nuclear magnetic resonance (NMR) spectroscopy was used for in situ analysis of illuminated light-active MMs. We found that the presence of a N , N -dimethylethylenediamine in a position conjugated to the central olefin results in changes to the rotation of a second-generation Feringa-type MM. Importantly, the addition decreases the photostability of the compound. The parent compound 1 can withstand >2 h of illumination with no signs of decomposition, while the amino 7 decomposes after 10 min. We found that the degradation can be mitigated by implementing the simple techniques of modulating the light dose, dilution, and stirring the sample while illuminating. Additionally, the presence of moisture affects the rate of the motor's rotation. The addition of the amino group to 1 , without moisture present, makes the rotation of motor 7 three times slower than the unfunctionalized parent compound. We also report the use of a method that can be used to determine the molar extinction coefficient of a light-generated metastable species. This method can be used when in situ NMR illumination is not available.

Antibiotic resistance is a growing health threat. There is an urgent and critical need to develop new antimicrobial modalities and therapies. Here, a set of hemithioindigo (HTI)-based molecular machines capable of specifically killing Gram-positive bacteria within minutes of activation with visible light (455 nm at 65 mW cm -2 ) that are safe for mammalian cells is described. Importantly, repeated exposure of bacteria to HTI does not result in detectable development of resistance. Visible light-activated HTI kill both exponentially growing bacterial cells and antibiotic-tolerant persister cells of various Gram-positive strains, including methicillin-resistant S. aureus (MRSA). Visible light-activated HTI also eliminate biofilms of S. aureus and B. subtilis in as little as 1 h after light activation. Quantification of reactive oxygen species (ROS) formation and protein carbonyls, as well as assays with various ROS scavengers, identifies oxidative damage as the underlying mechanism for the antibacterial activity of HTI. In addition to their direct antibacterial properties, HTI synergize with conventional antibiotics in vitro and in vivo, reducing the bacterial load and mortality associated with MRSA infection in an invertebrate burn wound model. To the best of the authors' knowledge, this is the first report on the antimicrobial activity of HTI-based molecular machines., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Various treatments based on drug administration and radiotherapy have been devoted to preventing, palliating, and defeating cancer, showing high efficiency against the progression of this disease. Recently, in this process, malignant cells have been found which are capable of triggering specific molecular mechanisms against current treatments, with negative consequences in the prognosis of the disease. It is therefore fundamental to understand the underlying mechanisms, including the genes-and their signaling pathway regulators-involved in the process, in order to fight tumor cells. Long non-coding RNAs, H19 in particular, have been revealed as powerful protective factors in various types of cancer. However, they have also evidenced their oncogenic role in multiple carcinomas, enhancing tumor cell proliferation, migration, and invasion. In this review, we analyze the role of lncRNA H19 impairing chemo and radiotherapy in tumorigenesis, including breast cancer, lung adenocarcinoma, glioma, and colorectal carcinoma.

Background: Acute stroke care has greatly improved in recent decades. However, the increasing stroke mortality in low-to-middle income countries suggests that progress has not been reached completely by these populations. Here we present the analysis of the hospital phase of the first population-based stroke surveillance study. Methods: A daily hospital surveillance method was used to identify adult patients with acute stroke during 18 months in six hospitals. We abstracted data on demographics, vascular risk factors, neuroimaging-confirmed stroke types, and clinical data. Results: A total of 1361 adults with acute stroke were identified (mean age 69.2 years; 52% women) with transient ischemic attack (5.5%), acute ischemic stroke (68.6%), intracerebral hemorrhage (23.1%), cerebral venous thrombosis (0.2%), and undetermined stroke (2.6%). The main risk factors were hypertension (80.7%) and diabetes mellitus (47.6%). The usage rate of thrombolysis was 3.6%, in spite of the fact that 37.2% of acute ischemic stroke patients arrived in <4.5 h. The 30-day case fatality rate was 32.6%, higher in hemorrhagic than ischemic stroke. Conclusion: We identified limitations in acute stroke care in the Mexico City, including neuroimaging availability and thrombolysis usage. The door-to-door phase will help to depict the acute stroke burden in Mexico.

By combining 3,6- N -ditriazolyl-2,5-dihydroxy-1,4-benzoquinone (H 2 trz 2 An) with NIR-emitting Er III ions, two different 3D neutral polymorphic frameworks (1a and 1b), differing in the number of uncoordinated water molecules, formulated as [Er 2 (trz 2 An) 3 (H 2 O) 4 ] n · x H 2 O ( x = 10, a; x = 7, b), have been obtained. The structure of 1a shows layers with (6,3) topology forming six-membered rings with distorted hexagonal cavities along the bc plane. These 2D layers are interconnected through the N4 atoms of the two pendant arms of the trz 2 An linkers, leading to a 3D framework, where neighboring layers are eclipsed along the a axis, with hexagonal channels filled with water molecules. In 1b, layers with (6,3) topology in the [101] plane are present, each Er III ion being connected to three other Er III ions through bis-bidentate trz 2 An linkers, forming rectangular six-membered cavities. 1a and 1b are multifunctional materials showing coexistence of NIR emission and field-induced slow relaxation of the magnetization. Remarkably, 1a is a flexible MOF, showing a reversible structural phase transition involving shrinkage/expansion from a distorted hexagonal 2D framework to a distorted 3,6-brickwall rectangular 3D structure in [Er 2 (trz 2 An) 3 (H 2 O) 2 ] n ·2H 2 O (1a&#95;des). This transition is triggered by a dehydration/hydration process under mild conditions (vacuum/heating to 360 K). The partially dehydrated compound shows a sizeable change in the emission properties and an improvement of the magnetic blocking temperature with respect to the hydrated compound, mainly related to the loss of one water coordination molecule. Theoretical calculations support the experimental findings, indicating that the slight improvement observed in the magnetic properties has its origin in the change of the ligand field around the Er III ion due to the loss of a water molecule., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The importance of the cytoskeleton not only in cell architecture but also as a pivotal element in the transduction of signals that mediate multiple biological processes has recently been highlighted. Broadly, the cytoskeleton consists of three types of structural proteins: (1) actin filaments, involved in establishing and maintaining cell shape and movement; (2) microtubules, necessary to support the different organelles and distribution of chromosomes during cell cycle; and (3) intermediate filaments, which have a mainly structural function showing specificity for the cell type where they are expressed. Interaction between these protein structures is essential for the cytoskeletal mesh to be functional. Furthermore, the cytoskeleton is subject to intense spatio-temporal regulation mediated by the assembly and disassembly of its components. Loss of cytoskeleton homeostasis and integrity of cell focal adhesion are hallmarks of several cancer types. Recently, many reports have pointed out that lncRNAs could be critical mediators in cellular homeostasis controlling dynamic structure and stability of the network formed by cytoskeletal structures, specifically in different types of carcinomas. In this review, we summarize current information available about the roles of lncRNAs as modulators of actin dependent cytoskeleton and their impact on cancer pathogenesis. Finally, we explore other examples of cytoskeletal lncRNAs currently unrelated to tumorigenesis, to illustrate knowledge about them.

Objective: After the acute period of infection by the SARS-CoV-2 virus (COVID-19), multi-organ signs and symptoms may remain. This study tried to compare the perception of the state of health and the sequelae in Navarra-Osasunbidea health workers after COVID-19, with the previous situation through the Health Survey., Methods: Through a descriptive cross-sectional study, using a reduced questionnaire from the 2017 National Health Survey sent to health workers from the Navarre-Osasunbidea Health Service COVID-19 cases after 3 and 6 months, from April to July 2021 and compared with 2017. Differences were described through means, percentages and prevalence ratio, with 95% confidence intervals., Results: Of 938 surveys sent, 93 of 3 months (46.3%) and 305 of 6 months (41.4%) were received, 87% of women and 13% of men and 43 years of average age and 64.3% were from nursing and 19.1% from medicine. The percentage that assessed their health status as good or very good was significantly lower at 6 months than health workers and the general population in 2017 (70.2% vs 80.4% and 75.5%), the limitation for the habitual activity (39.8% and 35.1% vs 18.3%), headache 2.7 times more frequent, the days of activity restriction (41.5 and 26.7 vs 7.5) and on bed. Mental health problems, concentration (45.2% and 43.9%), loss of sleep (44.1% and 43.3%) and consumption of tranquilizers and antidepressants (2 and 3 times more) stood out, although not of medical consultations., Conclusions: Navarre health workers diagnosed with COVID-19 in 2020 and early 2021 refer to the worst assessment of their health status at 3 and 6 months, greater limitation for usual activities, more frequent headaches and mental health problems, compared to the pre-pandemic period., Competing Interests: Disclosure The authors report no conflicts of interest in this work.

Van der Waals heterostructures (vdWHs) provide the possibility of engineering new materials with emergent functionalities that are not accessible in another way. These heterostructures are formed by assembling layers of different materials used as building blocks. Beyond inorganic 2D crystals, layered molecular materials remain still rather unexplored, with only few examples regarding their isolation as atomically thin layers. Here, the family of van der Waals heterostructures is enlarged by introducing a molecular building block able to produce strain: the so-called spin-crossover (SCO). In these metal-organic materials, a spin transition can be induced by applying external stimuli like light, temperature, pressure, or an electric field. In particular, smart vdWHs are prepared in which the electronic and optical properties of the 2D material (graphene and WSe 2 ) are clearly switched by the strain concomitant to the spin transition. These molecular/inorganic vdWHs represent the deterministic incorporation of bistable molecular layers with other 2D crystals of interest in the emergent fields of straintronics and band engineering in low-dimensional materials., (© 2022 Wiley-VCH GmbH.)

Deep whole genome and transcriptome sequencing have highlighted the importance of an emerging class of non-coding RNA longer than 200 nucleotides (i.e., long non-coding RNAs (lncRNAs)) that are involved in multiple cellular processes such as cell differentiation, embryonic development, and tissue homeostasis. Cancer is a prime example derived from a loss of homeostasis, primarily caused by genetic alterations both in the genomic and epigenetic landscape, which results in deregulation of the gene networks. Deregulation of the expression of many lncRNAs in samples, tissues or patients has been pointed out as a molecular regulator in carcinogenesis, with them acting as oncogenes or tumor suppressor genes. Herein, we summarize the distinct molecular regulatory mechanisms described in literature in which lncRNAs modulate carcinogenesis, emphasizing epigenetic and genetic alterations in particular. Furthermore, we also reviewed the current strategies used to block lncRNA oncogenic functions and their usefulness as potential therapeutic targets in several carcinomas.

Objective: The COVID-19 pandemic caused by the SARS-CoV-2 virus has generated a great burden on health systems, and healthcare workers have been the most affected. In Spain, the Health Ministry issued common protocols regarding the return-to-work of healthcare workers presenting a negative PCR (Polymerase Chain Reaction) test result and complete resolution of symptoms. Some autonomous communities decided to include a CT (Cycle Threshold) value criterion as well. The aim of this paper was to compare the time intervals required to obtain a negative PCR result by means of both criteria., Methods: A multicenter, cross-sectional study was performed from March to September of 2020, in the health areas of Navarra, La Rioja and Vigo (Galicia), managed by their own Occupational Risk Prevention Units. The PCR negativization time intervals were analyzed according to gender, age, professional category and the PCR repetition criteria used (clinical or defined by CT). Mean difference calculation by Student's t-test and Kaplan-Meier survival analyzes were conducted., Results: The sample amounted to a total of 1,052 workers: 673 from Navarra, 335 from La Rioja and 44 from Vigo, with an average age of 46 years, and of which 81% were women, 35.48% nursing personnel and 23.65% physicians. No statistically significant differences were found between the PCR negativization time periods with any of the variables, except with the CT criterion, which presented a mean of 6.49 days (95% CI, 4.96-8.02), longer and displaying positively displaced survival curves., Conclusions: The CT criterion for carrying out the control PCR test lengthened the reincorporation of essential personnel in the fight against the pandemic., Competing Interests: Disclosure The authors report no conflicts of interest in this work.

The synthesis of six 2,6-di(pyrazol-1-yl)pyridine derivatives bearing dithiolane or carboxylic acid tether groups is described: [2,6-di(pyrazol-1-yl)pyrid-4-yl]methyl (R)-lipoate (L1), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]ethyl (R)-lipoate (L2), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxy]ethyl (R)-lipoate (L3), N-([2,6-di(pyrazol-1-yl)pyrid-4-ylsulfanyl]-2-aminoethyl (R)-lipoamide (L4), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]acetic acid (L5) and 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]propionic acid (L6). The iron(ii) perchlorate complexes of all the new ligands exhibit gradual thermal spin-crossover (SCO) in the solid state above room temperature, except L4 whose complex remains predominantly high-spin. Crystalline [Fe(L6)2][ClO4]2·2MeCN contains three unique cation sites which alternate within hydrogen-bonded chains, and undergo gradual SCO at different temperatures upon warming. The SCO midpoint temperature (T1/2) of the complexes in CD3CN solution ranges between 208-274 K, depending on the functional group linking the tether groups to the pyridyl ring. This could be useful for predicting how these complexes might behave when deposited on gold or silica surfaces.

The commercialization of asbestos in Europe in the second half of the 20th century translated into consumption of millions of tons of this material. Occupational exposure to asbestos is controlled under the 2009 European Union Directive. Currently, through epidemiological surveillance and pathology registries (mainly mesotheliomas), it is possible to record past exposures. Despite prohibiting its use, large amounts of asbestos remain in buildings, infrastructures and vehicles, among others. The road to elimination of existing asbestos began with a 2013 European Parliament Resolution and the Opinion of the European Economic and Social Committee (2015 / C 251/03).To better understand barriers to implementing these plans, we reviewed the experience in Poland the only country that to date has implemented an action plan with great financial support, together with actions carried out in Spain generally, and Navarre specifically, given the latter's exhaustive registry of exposed workers.The enormous economic effort required to implement these plans, along with the environmental risks associated with asbestos abatement, require detailed planning, which should consider understanding why the objectives set by Poland, a benchmark country, have not been achieved to date., (Copyright belongs to the Associació Catalana de Salut Laboral.)

With the desire to synthesize surface-rolling molecular machines that can be translated and rotated with extreme precision and speed, we have synthesized a series of five nanocars. Each structure features a permanent dipole moment, generated by an N , N -dimethylamino- moiety on one end of the car coupled with a nitro group on the other end. These cars are designed to be stimulated with an electric field gradient from a scanning probe microscopy tip. The nanocars all possess unexplored combinations of structural features: tert -butyl wheels, short alkyne chassis, and combination sets of wheels including one set of tert -butyl wheels and another set of larger adamantane wheels on the same car. Each of these features needs to be assessed as preparation for the second International Nanocar Race that is taking place in 2022.

Resorcin[4]arene cavitands, equipped with diverse quinone (Q) and [Ru(bpy) 2 dppz] 2+ (bpy=2,2'-bipyridine, dppz=dipyrido[3,2-a:2',3'-c]phenazine) photosensitizing walls in different configurations, were synthesized. Upon visible-light irradiation at 420 nm, electron transfer from the [Ru(bpy) 2 dppz] 2+ to the Q generates the semiquinone (SQ) radical anion, triggering a large conformational switching from a flat kite to a vase with a cavity for the encapsulation of small guests, such as cyclohexane and heteroalicyclic derivatives, in CD 3 CN. Depending on the molecular design, the SQ radical anion can live for several minutes (≈10 min) and the vase can be generated in a secondary process without need for addition of a sacrificial electron donor to accumulate the SQ state. Switching can also be triggered by other stimuli, such as changes in solvent, host-guest complexation, and chemical and electrochemical processes. This comprehensive investigation benefits the development of stimuli-responsive nanodevices, such as light-activated molecular grippers., (© 2020 Wiley-VCH GmbH.)

Navarra has the first and most exhaustive Record of workers exposed to asbestos in Spain. Since 1996, referred by the Prevention Services and transferred to the Servicio Navarro de Salud&#95;Osasunbidea for related pulmonary pathology surveillance upon retirement. There are currently 2,858 workers, 395 women and 2,463 men. Almost no longer occupy positions of risk. For years it has helped to recognize the professional contingency of damages. Paradoxically, in this case, a worker who died of lung cancer with previous interstitial pathology, a negative result of an autopsy, 425ferruginous bodies/gr dry lung tissue was used to deny the professional origin. It is necessary to consider that a positive result confirms past exposure but the negative one should not be evaluated when it was chrysotile, given the low temporal persistence intissues. A reliable work history and, when they exist, the Records must be the main causal argument., (Copyright belongs to the Associació Catalana de Salut Laboral.)

Light-activated molecular nanomachines (MNMs) can be used to drill holes into prokaryotic (bacterial) cell walls and the membrane of eukaryotic cells, including mammalian cancer cells, by their fast rotational movement, leading to cell death. We examined how these MNMs function in multicellular organisms and investigated their use for treatment and eradication of specific diseases by causing damage to certain tissues and small organisms. Three model eukaryotic species, Caenorhabditis elegans , Daphnia pulex , and Mus musculus (mouse), were evaluated. These organisms were exposed to light-activated fast-rotating MNMs and their physiological and pathological changes were studied in detail. Slow rotating MNMs were used to control for the effects of rotation rate. We demonstrate that fast-rotating MNMs caused depigmentation and 70% mortality in C. elegans while reducing the movement as well as heart rate and causing tissue damage in Daphnia . Topically applied light-activated MNMs on mouse skin caused ulceration and microlesions in the epithelial tissue, allowing MNMs to localize into deeper epidermal tissue. Overall, this study shows that the nanomechanical action of light-activated MNMs is effective against multicellular organisms, disrupting cell membranes and damaging tissue in vivo . Customized MNMs that target specific tissues for therapy combined with spatial and temporal control could have broad clinical applications in a variety of benign and malignant disease states including treatment of cancer, parasites, bacteria, and diseased tissues.

Molecular motors are at the heart of cellular machinery, and they are involved in converting chemical and light energy inputs into efficient mechanical work. From a synthetic perspective, the most advanced molecular motors are rotators that are activated by light wherein a molecular subcomponent rotates unidirectionally around an axis. The mechanical work produced by arrays of molecular motors can be used to induce a macroscopic effect. Light activation offers advantages over biological chemically activated molecular motors because one can direct precise spatiotemporal inputs while conducting reactions in the gas phase, in solution and in vacuum, while generating no chemical byproducts or waste. In this review, we describe the origins of the first light-activated rotary motors and their modes of function, the structural modifications that led to newer motor designs with optimized rotary properties at variable activation wavelengths. Presented are molecular motor attachments to surfaces, their insertion into supramolecular structures and photomodulating materials, their use in catalysis, and their action in biological environments to produce exciting new prospects for biomedicine.

Objective: The aging of the working population is already a fact in Spain. International reference bodies (the ILO, the European Commission, the European Agency -EU&#95;OSHA- ...) and national organizations have begun to address this problem. Preventing and adapting working conditions to health problems linked to age is a fundamental task of the Occupational Risk Prevention Services (ORPS) although it is unknown to what extent it is being carried out. The objective of this study was to estimate how this emerging risk is being addressed., Methods: A descriptive, multicenter and crosssectional study was conducted based on the data provided by the ORPS of Public Administrations of three Autonomous Communities, Madrid, the Basque Country and Navarre, Period 2012-2016. The actions performed according to age, economic activity, occupation and size of the work center were analyzed by calculating distribution percentages and association analysis by Prevalence Ratios with 95% confidence intervals (95% CI)., Results: Information was collected from 14 ORPS, all with their own resources. In the majority (11 out of 14) age was not considered in either risk assessments or health surveillance. Small centers performed more frequently the adaptation of job, Risk of Prevalence 1.25 (95% CI 1.12-1.40). In those with more than 5,000 workers, the proportion of relocations was greater (9/1,000 vs 6/1,000). The age of 55 was the risk threshold. In addition to the risks inherent in the tasks, psychosocials were identified in all activities., Conclusions: Age is especially sensitive to occupational risks, it must be considered in the evaluation, as well as in the design and adaptation of jobs, a fundamental task of the ORPS., Competing Interests: Disclosure The authors report no conflicts of interest in this work.

The orientation of molecules is crucial in many chemical processes. Here, we report how single dipolar molecules can be oriented with maximum precision using the electric field of a scanning tunneling microscope. Rotation is found to occur around a fixed pivot point that is caused by the specific interaction of an oxygen atom in the molecule with the Ag(111) surface. Both directions of rotation are realized at will with 100% directionality. Consequently, the internal dipole moment of an individual molecule can be spatially mapped via its behavior in an applied electric field. The importance of the oxygen-surface interaction is demonstrated by the addition of a silver atom between a single molecule and the surface and the consequent loss of the pivot point.

We report a Fe(ii) complex based on 4',4'' carboxylic acid disubstituted dipyrazolylpyridine that shows a spin-crossover close to room temperature associated to a crystallographic phase transition and the LIESST effect with a high T(LIESST) of 120 K.

Two new heteroleptic complexes [Fe(1bppCOOH)(3bpp-bph)](ClO 4 ) 2 ·solv ( 1·solv , solv = various solvents; 1bppCOOH = 2,6-bis(1 H -pyrazol-1-yl)isonicotinic acid; 3bpp-bph = 2,6-bis(5-([1,1'-biphenyl]-4-yl)-1 H -pyrazol-3-yl)pyridine) and [Fe(1bppCOOH)(1bppCOOEt)](ClO 4 ) 2 ·0.5Me 2 CO ( 2·0.5Me 2 CO , 1bppCOOEt = ethyl 2,6-bis(1 H -pyrazol-1-yl)isonicotinate) were designed and prepared. The heteroleptic compound 1·solv was obtained by the combination of stoichiometric amounts of Fe(ClO 4 ) 2 , 1bppCOOH, and 3bpp-bph, and it was designed to fine-tune the spin crossover (SCO) properties with respect to the previously reported homoleptic compound [Fe(1bppCOOH) 2 ](ClO 4 ) 2 . Indeed, the introduction of a new substituted 3bpp ligand induces a weaker ligand field in addition to promoting the formation of π···π and C-H···π intermolecular interactions through the biphenyl groups. For the desolvated counterpart 1 , this results in a shift of the SCO curve toward room temperature and the observation of a 13 K hysteresis width. Besides, compound 2·0.5Me 2 CO , which represents the first example of a heteroleptic complex containing two 1bpp tridentate ligands, stabilizes the LS state at room temperature confirming the same trend observed for the corresponding homoleptic compounds. Interestingly, both 1 and 2·0.5Me 2 CO heteroleptic complexes exhibit photoswitchable properties when irradiating with a 523 nm laser at 10 K. Preliminary characterization of the deposited complexes on native SiO 2 by X-ray absorption measurements suggests oxidation and decomposition of the complexes.

Using two-photon excitation (2PE), molecular nanomachines (MNMs) are able to drill through cell membranes and kill the cells. This avoids the use of the more damaging ultraviolet light that has been used formerly to induce this nanomechanical cell-killing effect. Since 2PE is inherently confocal, enormous precision can be realized. The MNMs can be targeted to specific cell surfaces through peptide addends. Further, the efficacy was verified through a controlled opening of synthetic bilayer vesicles using the 2PE excitation of MNM that had been trapped within the vesicles.

Four new salts of the iron(ii) complex of the 2,6-bis(pyrazol-1-yl)pyridine ligand functionalized with a carboxylic acid group (bppCOOH) of formulas [Fe(bppCOOH)2](BF4)2 (1(BF4)2), [Fe(bppCOOH)2](CF3SO3)2·yMe2CO (1(CF3SO3)2·yMe2CO), [Fe(bppCOOH)2](AsF6)2·yMe2CO (1(AsF6)2·yMe2CO) and [Fe(bppCOOH)2](SbF6)2·yMe2CO (1(SbF6)2·yMe2CO) have been prepared and characterized together with a more complete structural and photomagnetic characterization of the previously reported [Fe(bppCOOH)2](ClO4)2 (1(ClO4)2). Furthermore, the iron(ii) complex of the ethyl ester derivative of bppCOOH (bppCOOEt) has been prepared and characterized (compound [Fe(bppCOOEt)2](ClO4)2·yMe2CO, 2(ClO4)2·yMe2CO). Isostructural 1(BF4)2 and 1(ClO4)2 show an abrupt and reversible spin transition with a much lower T1/2 for the BF4- salt. CF3SO3-, SbF6- and AsF6- counteranions and the bppCOOEt ligand lead to the incorporation of solvent molecules in the structures, which play an important role in the spin-crossover properties of these compounds. In the case of 1(CF3SO3)2·yMe2CO, a reversible spin transition is obtained after desolvation. All these compounds show a LIESST effect.

Objective: Although, occupational asthma (OA) causes great work disability, due to its diagnostic complexity, it is difficult to have it recognized by the official registration systems. To improve its detection, suspected systems have been developed. After years of experience in Navarre, we set out to characterize the suspected cases and compare them with those declared as an occupational disease (OD)., Methods: We identified the cases of OA reported as sentinel events in the Epidemiological Surveillance Program in Occupational Health in Navarra from January 2010 to December 2015 and the cases declared as OD (asthma). The population under study was the Navarra employed population (357,200 on average). In the cases with consent, the clinical and labor characteristics were compared with those of OD. Using the SPSS Statistics® 20v computer program, mean differences were calculated by the T test for independent samples and distribution percentage differences by Chi-square test, Fisher's exact test and nonparametric tests when application conditions were not satisfied. As an indicator of notification, the accumulated incidence per 100,000 workers was calculated for each year of program monitoring., Results: In the period, 79 sentinel events were reported (in 22 the investigation was concluded) and 50 cases of OD (24% relapses). We did not find statistically significant differences in age (41 vs. 40 years), nor gender (40.9% women vs. 44.7%), nor proportion that caused sick leave (45% and 36.8%), nor size, activity of the company or occupation of the worker. Where differences are found was in the meantime of exposure before the recognition/notification, significantly higher in the OD than in the sentinel (94.1 vs. 22.2 months), 72 months longer., Conclusions: The cases detected by both systems are similar but, due to the diagnostic complexity, the recognition is delayed as OD, which demonstrates the usefulness of a more agile system for reporting suspicions of this work pathology., Competing Interests: Disclosure The authors report no conflicts of interest in this work.