Host-Guest Stimuli-Responsive Click Chemistry.

Click chemistry has reached its maturity as the weapon of choice for the irreversible ligation of molecular fragments, with over 20 years of research resulting in the development or improvement of highly efficient kinetically controlled conjugation reactions. Nevertheless, traditional click reactions can be disadvantageous not only in terms of efficiency (side products, slow kinetics, air/water tolerance, etc.), but also because they completely avoid the possibility to reversibly produce and control bound/unbound states. Recently, non-covalent click chemistry has appeared as a more efficient alternative, in particular by using host-guest self-assembled systems of high thermodynamic stability and kinetic lability. This review discusses the implementation of molecular switches in the development of such non-covalent ligation processes, resulting in what we have termed stimuli-responsive click chemistry, in which the bound/unbound constitutional states of the system can be favored by external stimulation, in particular using host-guest complexes. As we exemplify with handpicked selected examples, these supramolecular systems are well suited for the development of human-controlled molecular conjugation, by coupling thermodynamically regulated processes with appropriate temporally resolved extrinsic control mechanisms, thus mimicking nature and advancing our efforts to develop a more function-oriented chemical synthesis.

Potential for host-symbiont communication via neurotransmitters and neuromodulators in an aneural animal, the marine sponge Amphimedon queenslandica.

Interkingdom signalling within a holobiont allows host and symbionts to communicate and to regulate each other's physiological and developmental states. Here we show that a suite of signalling molecules that function as neurotransmitters and neuromodulators in most animals with nervous systems, specifically dopamine and trace amines, are produced exclusively by the bacterial symbionts of the demosponge Amphimedon queenslandica. Although sponges do not possess a nervous system, A. queenslandica expresses rhodopsin class G-protein-coupled receptors that are structurally similar to dopamine and trace amine receptors. When sponge larvae, which express these receptors, are exposed to agonists and antagonists of bilaterian dopamine and trace amine receptors, we observe marked changes in larval phototactic swimming behaviour, consistent with the sponge being competent to recognise and respond to symbiont-derived trace amine signals. These results indicate that monoamines synthesised by bacterial symbionts may be able to influence the physiology of the host sponge.

Finger-Actuated Micropump of Constant Flow Rate without Backflow.

This paper presents a finger-actuated micropump with a consistent flow rate and no backflow. The fluid dynamics in interstitial fluid (ISF) extraction microfluidics are studied through analytical, simulation, and experimental methods. Head losses, pressure drop, diodocity, hydrogel swelling, criteria for hydrogel absorption, and consistency flow rate are examined in order to access microfluidic performance. In terms of consistency, the experimental result revealed that after 20 s of duty cycles with full deformation on the flexible diaphragm, the output pressure became uniform and the flow rate remained at nearly constant levels of 2.2 µL/min. The flow rate discrepancy between the experimental and predicted flow rates is around 22%. In terms of diodicity, when the serpentine microchannel and hydrogel-assisted reservoir are added to the microfluidic system integration, the diodicity increases by 2% (Di = 1.48) and 34% (Di = 1.96), respectively, compared to when the Tesla integration (Di = 1.45) is used alone. A visual and experimentally weighted analysis finds no signs of backflow. These significant flow characteristics demonstrate their potential usage in many low-cost and portable microfluidic applications.

Establishment of reference intervals for complete blood count in times of COVID-19 and vaccination.

Introduction: COVID-19 and vaccination may affect some parameters of the complete blood count (CBC). The aim of this study was to determine reference intervals (RI) of CBC in healthy population with different COVID-19 and vaccination backgrounds and compare them with those established previously. Materials and methods: A cross-sectional study was conducted in donors who attended the Traumatology Hospital "Dr. Victorio de la Fuente Narváez" (HTVFN) from June to September 2021. Reference intervals were established using the non-parametric method on Sysmex XN-1000. For differences between groups with different COVID-19 and vaccination backgrounds, non-parametric tests were used. Results: The RI were established in 156 men and 128 women. Haemoglobin (Hb), haematocrit (Hct), red blood cells (RBC), platelets (Plt), mean platelets volume (MPV), monocytes and relative neutrophils were higher in men than women (P < 0.001). The percentiles of Hb, Hct, RBC, MPV and relative monocytes showed higher values; Plt, white blood cells (WBC), lymphocytes, monocytes, neutrophils, eosinophils and absolute basophils, the 2.5th was higher and the 97.5th was lower; for lymphocytes and relative neutrophils, both percentiles had a trend toward lower values, compared to previous RI. Differences between groups with different COVID-19 and vaccination backgrounds, in lymphocytes (P = 0.038), neutrophils (P = 0.017) and eosinophils (P = 0.018) in men; Hct (P = 0.014), RDW (P = 0.023) in women and MPV (P = 0.001) in both, were not considered pathological. Conclusions: The RI for the CBC were established in a Mestizo-Mexican population with different COVID-19 and vaccination backgrounds, so should be updated and validated in different hospitals close to the HTVFN that use the same analyser.

Aqueous Three-Component Self-Assembly of a Pseudo[1]rotaxane Using Hydrazone Bonds.

We present herein the synthesis of a new polycationic pseudo[1]rotaxane, self-assembled in excellent yield through hydrazone bonds in aqueous media of three different aldehyde and hydrazine building blocks. A thermodynamically controlled process has been studied sequentially by analyzing the [1 + 1] reaction of a bisaldehyde and a trishydrazine leading to the macrocyclic part of the system, the ability of this species to act as a molecular receptor, the conversion of a hydrazine-pending cyclophane into the pseudo[1]rotaxane and, lastly, the one-pot [1 + 1 + 1] condensation process. The latter was found to smoothly produce the target molecule through an integrative social self-sorting process, a species that was found to behave in water as a discrete self-inclusion complex below 2.5 mM concentration and to form supramolecular aggregates in the 2.5-70 mM range. Furthermore, we demonstrate how the abnormal kinetic stability of the hydrazone bonds on the macrocycle annulus can be advantageously used for the conversion of the obtained pseudo[1]rotaxane into other exo-functionalized macrocyclic species.

Fabrication of Li-Doped NiO Thin Films by Ultrasonic Spray Pyrolysis and Its Application in Light-Emitting Diodes.

The fabrication of NiO films by different routes is important to extend and improve their applications as hole-transporting layers in organic and inorganic optoelectronic devices. Here, an automated ultrasonic pyrolysis spray method was used to fabricate NiO and Li-doped NiO thin films using nickel acetylacetonate and lithium acetate dihydrate as metal precursor and dimethylformamide as solvent. The effect of the amount of lithium in the precursor solution on the structural, morphological, optical, and electrical properties were studied. XRD results reveal that all the samples are polycrystalline with cubic structure and crystallite sizes in the range of 21 to 25 nm, without any clear trend with the Li doping level. AFM analysis shows that the crystallites form round-shaped aggregates and all the films have low roughness. The optical transmittance of the films reaches values of 60% to 77% with tendency upward as Li content is increased. The electrical study shows that the films are p-type, with the carrier concentration, resistivity, and carrier mobility depending on the lithium doping. NiO:Li (10%) films were successfully incorporated into inorganic light emitting diodes together with Mn-doped ZnS and ZnO:Al films, all deposited on ITO by the same ultrasonic spray pyrolysis technique.

New approaches to epidemic modeling on networks.

In this article, we develop two independent and new approaches to model epidemic spread in a network. Contrary to the most studied models, those developed here allow for contacts with different probabilities of transmitting the disease (transmissibilities). We then examine each of these models using some mean field type approximations. The first model looks at the late-stage effects of an epidemic outbreak and allows for the computation of the probability that a given vertex was infected. This computation is based on a mean field approximation and only depends on the number of contacts and their transmissibilities. This approach shares many similarities with percolation models in networks. The second model we develop is a dynamic model which we analyze using a mean field approximation which highly reduces the dimensionality of the system. In particular, the original system which individually analyses each vertex of the network is reduced to one with as many equations as different transmissibilities. Perhaps the greatest contribution of this article is the observation that, in both these models, the existence and size of an epidemic outbreak are linked to the properties of a matrix which we call the [Formula: see text]-matrix. This is a generalization of the basic reproduction number which more precisely characterizes the main routes of infection.

Alzheimer and Parkinson diseases, frontotemporal lobar degeneration and amyotrophic lateral sclerosis overlapping neuropathology start in the first two decades of life in pollution exposed urbanites and brain ultrafine particulate matter and industrial nanoparticles, including Fe, Ti, Al, V, Ni, Hg, Co, Cu, Zn, Ag, Pt, Ce, La, Pr and W are key players. Metropolitan Mexico City health crisis is in progress.

The neuropathological hallmarks of Alzheimer's disease (AD), Parkinson's disease (PD), frontotemporal lobar degeneration (FTLD), and amyotrophic lateral sclerosis (ALS) are present in urban children exposed to fine particulate matter (PM2.5), combustion and friction ultrafine PM (UFPM), and industrial nanoparticles (NPs). Metropolitan Mexico City (MMC) forensic autopsies strongly suggest that anthropogenic UFPM and industrial NPs reach the brain through the nasal/olfactory, lung, gastrointestinal tract, skin, and placental barriers. Diesel-heavy unregulated vehicles are a key UFPM source for 21.8 million MMC residents. We found that hyperphosphorylated tau, beta amyloid1-42, α-synuclein, and TAR DNA-binding protein-43 were associated with NPs in 186 forensic autopsies (mean age 27.45 ± 11.89 years). The neurovascular unit is an early NPs anatomical target, and the first two decades of life are critical: 100% of 57 children aged 14.8 ± 5.2 years had AD pathology; 25 (43.9%) AD+TDP-43; 11 (19.3%) AD + PD + TDP-43; and 2 (3.56%) AD +PD. Fe, Ti, Hg, Ni, Co, Cu, Zn, Cd, Al, Mg, Ag, Ce, La, Pr, W, Ca, Cl, K, Si, S, Na, and C NPs are seen in frontal and temporal lobes, olfactory bulb, caudate, substantia nigra, locus coeruleus, medulla, cerebellum, and/or motor cortical and spinal regions. Endothelial, neuronal, and glial damages are extensive, with NPs in mitochondria, rough endoplasmic reticulum, the Golgi apparatus, and lysosomes. Autophagy, cell and nuclear membrane damage, disruption of nuclear pores and heterochromatin, and cell death are present. Metals associated with abrasion and deterioration of automobile catalysts and electronic waste and rare earth elements, i.e., lanthanum, cerium, and praseodymium, are entering young brains. Exposure to environmental UFPM and industrial NPs in the first two decades of life are prime candidates for initiating the early stages of fatal neurodegenerative diseases. MMC children and young adults-surrogates for children in polluted areas around the world-exhibit early AD, PD, FTLD, and ALS neuropathological hallmarks forecasting serious health, social, economic, academic, and judicial societal detrimental impact. Neurodegeneration prevention should be a public health priority as the problem of human exposure to particle pollution is solvable. We are knowledgeable of the main emission sources and the technological options to control them. What are we waiting for?

Desarrollo de una Escala de Calidad de la Información transmitida por Medios de Comunicación Electrónicos (ECIME) / Development of a Quality Information Scale broadcasted by Electronic Media (QISEM)

Resumen La producción de la información, en relación con su calidad dentro de la práctica periodística en general, está supeditada a diversos criterios, como la veracidad de la fuente, la acreditación de los autores, la comprensión del texto y la relevancia de la información, entre otros indicadores. El objetivo del presente trabajo fue desarrollar una escala para evaluar la calidad de la información transmitida por medios de comunicación en Internet. Para ello, se realizaron tres etapas generales: la primera estuvo conformada por 13 estudios, donde, después de un análisis de contenido, se extrajeron las dimensiones o aspectos de la calidad de la información más frecuentemente mencionados. Posteriormente, se procedió a la detección de 35 indicadores, clasificados en 5 dimensiones; en la segunda se obtuvieron 65 ítems, a partir de la clasificación de 5 dimensiones y los 35 indicadores; en la tercera se pilotó el instrumento obtenido, el cual adquirió un formato de lista de verificación integrado por 38 ítems, y con el propósito de determinar la validez de discriminación y la confiabilidad de la escala, se aplicó a una muestra no aleatoria de 100 noticias sobre COVID-19, publicadas en sitios de internet durante el 21 de enero de 2020 y el 31 de julio de 2021. La escala desarrollada permitió evaluar la calidad de la información que se transmite por medios de comunicación electrónicos, por lo que puede ser utilizada para mejorar las prácticas de los encargados de construir el contenido informativo y divulgarlo.

Abstract Information production, regarding its quality within journalistic practice in general, is subject to various criteria, such as the veracity of the source, the accreditation of the authors, the understanding of the text, and the relevance of the information, among other indicators. The objective of the present work was to develop a scale to assess the quality of information broadcasted by media on the Internet. To achieve this goal, three general stages were carried out: the first consisted of 13 studies, where, after a content analysis, the most frequently mentioned quality information dimensions were extracted. Subsequently, 35 indicators classified in 5 dimensions were detected. In the second stage, 65 items were obtained from the classification of 5 dimensions and 35 indicators. In the third stage, the obtained instrument was piloted. The instrument acquired a checklist format made up of 38 items. To determine the discrimination validity and the reliability of the scale, it was applied to a non-random sample of 100 COVID-19 news posted on internet sites from January 21st, 2020, to July 31, 2021. The developed scale allowed the evaluation of the quality of information broadcasted by electronic media, it can therefore be used to improve the practices of those in charge of constructing the informative content and disseminating it.

Guillain-Barré syndrome outbreak in Tapachula temporally associated with the Zika virus introduction in Southern Mexico.

The Guillain-Barré syndrome (GBS) has been previously associated with Zika virus infection. We analysed the data from all the patients with GBS diagnosis that were admitted to a referral hospital, in Tapachula City during the period from January 2013 to August 2016, comparing the incidence of GBS according to the temporality of the Zika outbreak in Southern Mexico. Additionally, we described the clinical and epidemiological characteristics of the GBS patients admitted before or after the Zika outbreak. We observed a sharp increase in the number of patients hospitalised due to GBS from the time the first confirmed Zika cases appeared in Mexico. Clinically we observed GBS cases before zika outbreak had more frequently history of respiratory/gastrointestinal symptoms and GBS during zika outbreak had significantly more frequently recent history of rash/conjunctivitis. Although we cannot affirm that the increased cases of GBS have a specific aetiologic association with Zika, our results suggest that this observed outbreak of in Tapachula, might have been associated to the emerging Zika epidemic, locally and suggests that rare complications associated with acute infections (such as GBS) might be useful in the surveillance systems for emerging infections.

"Vermellogens" and the Development of CB[8]-Based Supramolecular Switches Using pH-Responsive and Non-Toxic Viologen Analogues.

We present herein the "vermellogens", a new class of pH-responsive viologen analogues, which replace the direct linking between para-substituted pyridinium moieties within those by a hydrazone functional group. A series of such compounds have been efficiently synthesized in aqueous media by hydrazone exchange reactions, displaying a marked pH-responsivity. Furthermore, the parent N,N'-dimethylated "vermellogen": the "red thread", an analogue of the herbicide paraquat and used herein as a representative model of the series, showed anion-recognition abilities, non-reversible electrochemical behavior, and non-toxicity of the modified bis-pyridinium core. The host-guest chemistry for the "red thread" with the CB[7,8] macrocyclic receptors has been extensively studied experimentally and by dispersion corrected density functional theory methods, showing a parallel behavior to that previously described for the herbicide but, crucially, swapping the well-known redox reactive capabilities of the viologen-based inclusion complexes by acid-base supramolecular responsiveness.

Diesel effects on some population attributes of Orthonychiurus folsomi Schäffer 1900 (Collembola: Onychiuridae) under laboratory conditions.

Soil contamination by hydrocarbons and its effects on population health and welfare is a growing concern, especially in urban environments with industrial activity. Indicator species complement the information obtained from the measurement of environment quality by using physicochemical variables. The objective of this study was to evaluate the response of a springtail species that could be potentially used as a bioindicator of hydrocarbon contaminated sites. We studied the effects of seven diesel concentrations on survival and other population parameters of Orthonychiurus folsomi under laboratory conditions; we evaluated the springtails response on survival, fecundity, population size, hatching and development time. Survival and fertility were analyzed by using generalized linear models (GLM). An ANOVA test was used to analyze the final population size and a Kruskal-Wallis test for oviposition, hatching, and development times. Results showed that diesel has negative effects on some population parameters. The most evident effects were recorded above 500 mg/kg concentrations. A significant decrease in survival, fertility, and population size was recorded in function of diesel concentration increase. The estimated LC50 for survival was 955 mg/kg. Oviposition and hatching time increased significantly when diesel concentrations were above 500 mg/kg, while development time increased slightly at low diesel concentrations but decreased at concentrations above 500 mg/kg. Population final size decreased as soil diesel concentrations increased. Due to the sensitive and rapid response of O. folsomi, it could be useful to detect diesel-contaminated soil, mainly in urban areas.

Experimental Study of the Influence of CH4 and H2 on the Conformation, Chemical Composition, and Luminescence of Silicon Quantum Dots Inlaid in Silicon Carbide Thin Films Grown by Remote Plasma-Enhanced Chemical Vapor Deposition.

Silicon carbide (SiC) has become an extraordinary photonic material. Achieving reproducible self-formation of silicon quantum dots (SiQDs) within SiC matrices could be beneficial for producing electroluminescent devices operating at high power, high temperatures, or high voltages. In this work, we use a remote plasma-enhanced chemical vapor deposition system to grow SiC thin films. We identified that a particular combination of 20 sccm of CH4 and a range of 58-100 sccm of H2 mass flow with 600 °C annealing allows the abundant and reproducible self-formation of SiQDs within the SiC films. These SiQDs dramatically increase the photoluminescence-integrated intensity of our SiC films. The photoluminescence of our SiQDs shows a normal distribution with positive skewness and well-defined intensity maxima in blue regions of the electromagnetic spectrum (439-465 nm) and is clearly perceptible to the naked eye.

Surgery of neurogenic tumors of the sacrum.

OBJECTIVES: Our objective is to share our experience in neurogenic tumors of the sacral area, an uncommon disease, and assess approaches, intraoperative techniques, complications and clinical course of patients in a case series. METHODS: We conducted a retrospective analysis of 19 cases of patients with neurogenic tumors in the sacral area who were diagnosed and underwent surgery at our center. Of them, 8 were male and 11 were female. They had a mean age at diagnosis of 51 years (with an age range of 25-78 years). Six patients were asymptomatic and were diagnosed incidentally, while the majority (11 patients) presented with lumbar pain accompanied by other symptoms: pain radiating to the legs, pelvic pain, sensory alterations and loss of strength in the legs. Two patients presented with another primary symptom on diagnosis: pain in the pelvic region and in the left leg. All patients underwent a least one imaging test (MRI/CT scan). Nine patients had tumors limited to the sacrum or with subsequent spread, with surgery via the posterior route. In 6 cases, an exclusively anterior approach was employed owing to the pre-sacral location of the tumor; 4 cases required both an anterior and posterior approach. RESULTS: The 6 patients who were asymptomatic at diagnosis continued to have no symptoms after surgery. In 8 patients, symptoms resolved after surgery, and at discharge 4 had pain in the lumbar region or legs, which improved in subsequent consultations. One patient had symptoms consistent with motor and sensory deficit in the right leg deriving from impairment of the external popliteal sciatic nerve. The mean follow-up period was 69 months (6-178 months). Histologically, 17 cases were classified as schwannomas, one case was classified as neurofibroma, and one case was classified as neurofibrosarcoma, which received radiotherapy. Three patients with benign histologies had further surgery for local recurrences. CONCLUSIONS: When selecting the approach, the large size that these tumors can reach, their relationship with structures, and their anterior or posterior spread should be taken in to account. Resecting the tumor mass as much as possible provides greater benefit to the patient, as this decreases the odds of tumor recurrence without increasing intraoperative and postoperative complications when multidisciplinary teams are also used.

Four new species of Parajapyx (Diplura: Parajapygidae) from Mexico with redescription of Parajapyx isabellae aztecus Silvestri.

Four new Mexican Parajapyx species are described: P. silvestrii sp. nov. differs from P. adisi Pagés by the presence of one ma macroseta on mesoscutum, metascutum and abdominal scutum I; P. pagesi sp. nov. differs from P. grassianus Silvestri in the arrangement and number of macrosetae on all abdominal scuta; P. brunocondei sp. nov. is characterized by the unique feature of 50 glandular setae on the subcoxal organs and femur with one macroseta; P. yunyanorum sp. nov. differs from P. reymi Pagés by having some reduced macrosetae on the mesoscutum and metascutum and one lp macroseta lacking on abdominal II to VII scuta. A redescription of P. isabellae aztecus Silvestri, 1948 is presented including additional characters not previously reported, such as complete body chaetotaxy and descriptions of leg III, antennae and cercus. An identification key is presented for Mexican species of Parajapyx.

Self-Assembly of Pseudo[1]rotaxanes by Palladium(II)/Platinum(II)-Directed Integrative Social Self-Sorting: Is the Metal Required?

New results are presented on the multicomponent supramolecular synthesis of pseudo[1]rotaxanes, achieved by designing pairs of structurally matching N-monoalkyl-4,4'-bipyridinium/2,7-diazapyrenium-based ligands having complementary π-donor/acceptor features, and intended to self-assemble into the targeted supramolecules by following integrative self-sorting processes. In all the studied cases, it was found that the envisioned species, characterized by NMR spectroscopy and MS spectrometry, arise as the main products of the self-assembly in aqueous media by using palladium(II)/platinum(II) metal centers as the guiding force. Crucially, we have also found that by improving the π-donor/acceptor properties of the matching pairs of ligands (L4 and L5 ), the integrative self-sorting processes prevail even in the absence of metallic ions to afford the heterodimeric species with an association constant being 756±43 M-1 .

Surgery of neurogenic tumors of the sacrum. / Cirugía de los tumores neurales del sacro.

OBJECTIVES: Our objective is to share our experience in neurogenic tumors of the sacral area, an uncommon disease, and assess approaches, intraoperative techniques, complications and clinical course of patients in a case series. METHODS: We conducted a retrospective analysis of 19 cases of patients with neurogenic tumors in the sacral area who were diagnosed and underwent surgery at our center. Of them, 8 were male and 11 were female. They had a mean age at diagnosis of 51 years (with an age range of 25-78 years). Six patients were asymptomatic and were diagnosed incidentally, while the majority (11 patients) presented with lumbar pain accompanied by other symptoms: pain radiating to the legs, pelvic pain, sensory alterations and loss of strength in the legs. Two patients presented with another primary symptom on diagnosis: pain in the pelvic region and in the left leg. All patients underwent a least one imaging test (MRI/CT scan). Nine patients had tumors limited to the sacrum or with subsequent spread, with surgery via the posterior route. In 6 cases, an exclusively anterior approach was employed owing to the pre-sacral location of the tumor; 4 cases required both an anterior and posterior approach. RESULTS: The 6 patients who were asymptomatic at diagnosis continued to have no symptoms after surgery. In 8 patients, symptoms resolved after surgery, and at discharge 4 had pain in the lumbar region or legs, which improved in subsequent consultations. One patient had symptoms consistent with motor and sensory deficit in the right leg deriving from impairment of the external popliteal sciatic nerve. The mean follow-up period was 69 months (6-178 months). Histologically, 17 cases were classified as schwannomas, one case was classified as neurofibroma, and one case was classified as neurofibrosarcoma, which received radiotherapy. Three patients with benign histologies had further surgery for local recurrences. CONCLUSIONS: When selecting the approach, the large size that these tumors can reach, their relationship with structures, and their anterior or posterior spread should be taken in to account. Resecting the tumor mass as much as possible provides greater benefit to the patient, as this decreases the odds of tumor recurrence without increasing intraoperative and postoperative complications when multidisciplinary teams are also used.

Dissecting the "Blue Box": Self-Assembly Strategies for the Construction of Multipurpose Polycationic Cyclophanes.

Stoddart's "blue box" (B4+), is one of the most iconic molecules in the recent history of chemistry. This rectangular tetracationic cyclophane has not only the ability to complex a wide variety of aromatic guests in organic or aqueous media, but because of the presence of viologen units on its structure, it also behaves as a redox-based molecular switch. In turn, B4+-based host-guest complexes can translate this responsiveness from the molecular to the supramolecular level, resulting in host-controlled binding. This unique behavior has allowed the development of a wide variety of B4+-containing (supra)molecular switches and machines, which certainly have inspired a whole generation of supramolecular chemists. Nevertheless, issues, such as synthetic accessibility, structural diversity, or the implementation of new chemical properties (luminescence, pH- or photo-responsiveness, etc.), have restricted somehow the development of new practical applications in the ever-changing realm of modern host-guest chemistry.Based largely on our own research throughout the past decade, we will highlight in this account two different strategies for the self-assembly of new B4+ analogues: (1) Pd(II)/Pt(II) metal-directed self-assembly and (2) hydrazone-based dynamic covalent chemistry. In essence, the strategies are based on the substitution of inert C-C single bonds on the macrocycle by Pd/Pt-N or C═N bonds of modifiable lability. In the case of the metal-directed synthesis, the use of Pd(II) centers allows for the spontaneous self-assembly at r.t., either in organic or aqueous media, of N-alkyl-4,4'-bipyridinium-based ligands into the desired metallacycles. Conversely, more inert Pt(II) salts can be also implemented, rendering the synthesis of more kinetically stable analogues. Alternatively, wholly organic B4+ congeners can be produced in a modular fashion by using hydrazone-based dynamic covalent chemistry, allowing for the self-assembly in acidic water of macrocyclic pH-responsive molecular switches of adjustable kinetic stability.Owning pyridinium-based cavities of appropriate size, our B4+-inspired cyclophanes are able to complex aromatic substrates by a conjunction of the hydrophobic effect and π-π/C-H···π interactions. Consequently, we will discuss in detail the different host-guest complexes that can be achieved using our cyclophanes. Considering this knowledge, the implementation of our B4+-based macrocycles onto mechanically interlocked molecules and knots will be introduced, as well as the development of practical applications for the hosts in currently important research fields, such as the development of duplex and G4-DNA binders, supramolecular catalysis or the sequestration of relevant pollutants. Finally, self-assembled hosts offer the unique opportunity to include constitutional dynamism into host-guest chemistry, so examples of the development by our group of stimuli-responsive constitutionally dynamic libraries and self-sorted systems will be highlighted.

Influence of Calcium Scaling on Corrosion Behavior of Steel and Aluminum Alloys.

Calcium scaling is a serious problem encountered in the oil and gas industry because it is common that brines produced alongside oil and gas exhibit high concentrations of calcium ions, among others, which is expensive to remedy. The precipitation of calcium salts on the internal wall of the pipelines may occur because of the physical and chemical changes as fluids are produced from downhole to surface facilities. Although different researchers have address scaling and corrosion in the oil and gas industry, there are few reports in the literature relating the corrosion and scaling phenomena simultaneously. Despite there being indications that scales may produce corrosion problems, affecting the mechanical integrity of the infrastructure, there is minimal research in the literature addressing such relations. Previous studies presented aluminum alloys as excellent and reliable materials for applications in the petroleum industry, such as drilling activities. In this work, we evaluate the corrosion behavior of steel and aluminum alloys under highly scaling environments using supersaturated brines. Our results show that the presence of calcium carbonate and calcium sulfate as a scaling environment increases the corrosion rates for aluminum alloys and carbon steel; however, the same environments do not affect the corrosion behavior of stainless steel.

Controlled binding of organic guests by stimuli-responsive macrocycles.

Synthetic supramolecular chemistry pursues not only the construction of new matter, but also control over its inherently dynamic behaviour. In this context, classic host-guest chemistry, based on the development of a myriad of macrocyclic receptors with fine-tuned affinities and selectivities, has enormously contributed to the discovery of new chemical function under self-assembly conditions. In turn, the use of molecular switches as control units within host-guest assemblies opened the door for the regulation of their dynamic interactional behaviour, which can be translated into controlled aggregation. In this review, we will focus on different strategies developed for the regulated binding of organic molecules by switchable macrocyclic hosts. As we will see, an appropriate design using stimuli-responsive versions of well-known organic receptors allows the molecular switches implemented within their structures to transform their regulated behaviour from the molecular to the supramolecular level.