Cryoprotective Polysaccharides with Ordered Gel Structures Induce Ice Growth Anticipation and Survival Enhancement during Cell Cryopreservation.

This work cross-correlated rheological, thermodynamic, and conformational features of several natural polysaccharides to their cryoprotective performance. The basis of cryoprotection of FucoPol, pectin, and agar revealed a causal combination of (i) an emerging sol-gel transition (p = 0.014) at near-hypothermia (4 °C), (ii) noncolligative attenuated supercooling of the kinetic freezing point of water (p = 0.026) supporting ice growth anticipation, and (iii) increased conformational order (p < 0.0001), where helix-/sheet-like features boost cryoprotection. FucoPol, of highest cryoprotective performance, revealed a predominantly helical structure (α/ß = 1.5) capable of forming a gel state at 4 °C and the highest degree of supercooling attenuation (TH = 6.2 °C). Ice growth anticipation with gel-like polysaccharides suggests that the gel matrix neutralizes elastic deformations and lethal cell volumetric fluctuations during freezing, thus preventing the loss of homeostasis and increasing post-thaw viability. Ultimately, structured gels capable of attenuated supercooling enable cryoprotective action at the polymer-cell interface, in addition to polymer-ice interactions. This rationale potentiates implementing alternative, biobased, noncytotoxic polymers in cryobiology.

The aquaculture supply chain in the time of covid-19 pandemic: Vulnerability, resilience, solutions and priorities at the global scale.

The COVID-19 global pandemic has had severe, unpredictable and synchronous impacts on all levels of perishable food supply chains (PFSC), across multiple sectors and spatial scales. Aquaculture plays a vital and rapidly expanding role in food security, in some cases overtaking wild caught fisheries in the production of high-quality animal protein in this PFSC. We performed a rapid global assessment to evaluate the effects of the COVID-19 pandemic and related emerging control measures on the aquaculture supply chain. Socio-economic effects of the pandemic were analysed by surveying the perceptions of stakeholders, who were asked to describe potential supply-side disruption, vulnerabilities and resilience patterns along the production pipeline with four main supply chain components: a) hatchery, b) production/processing, c) distribution/logistics and d) market. We also assessed different farming strategies, comparing land- vs. sea-based systems; extensive vs. intensive methods; and with and without integrated multi-trophic aquaculture, IMTA. In addition to evaluating levels and sources of economic distress, interviewees were asked to identify mitigation solutions adopted at local / internal (i.e., farm-site) scales, and to express their preference on national / external scale mitigation measures among a set of a priori options. Survey responses identified the potential causes of disruption, ripple effects, sources of food insecurity, and socio-economic conflicts. They also pointed to various levels of mitigation strategies. The collated evidence represents a first baseline useful to address future disaster-driven responses, to reinforce the resilience of the sector and to facilitate the design reconstruction plans and mitigation measures, such as financial aid strategies.

Charged pullulan derivatives for the development of nanocarriers by polyelectrolyte complexation.

Pullulan, a neutral polysaccharide, was chemically modified in order to obtain two charged derivatives: reaction with SO3(.)DMF complex afforded a sulfate derivative (SP), while reaction with glycidyltrimethylammonium chloride gave a quaternary ammonium salt (AP). The presence of the charged groups was confirmed by FTIR. Assessment of the positions where the reaction took place was based on (1)H- and (13)C NMR (COSY, HSQC-TOCSY, HSQC-DEPT, and HMBC) experiments. Estimation of the degree of substitution (DS) was made from elemental analysis data, and further confirmed by NMR peak areas in the case of AP. These new derivatives showed the capability to condense with each other, forming nanoparticles with the ability to associate a model protein (BSA) and displaying adequate size for drug delivery applications, therefore making them good candidates for the production of pullulan-based nanocarriers by polyelectrolyte complexation.

Treatment of Cancer Pain by Targeting Cytokines.

Inflammation is one of the most important causes of the majority of cancer symptoms, including pain, fatigue, cachexia, and anorexia. Cancer pain affects 17 million people worldwide and can be caused by different mediators which act in primary efferent neurons directly or indirectly. Cytokines can be aberrantly produced by cancer and immune system cells and are of particular relevance in pain. Currently, there are very few strategies to control the release of cytokines that seems to be related to cancer pain. Nevertheless, in some cases, targeted drugs are available and in use for other diseases. In this paper, we aim to review the importance of cytokines in cancer pain and targeted strategies that can have an impact on controlling this symptom.

Dipolar motions and ionic conduction in an ibuprofen derived ionic liquid.

It was demonstrated that the combination of the almost water insoluble active pharmaceutical ingredient (API) ibuprofen with the biocompatible 1-ethanol-3-methylimidazolium [C2OHMIM] cation of an ionic liquid (IL) leads to a highly water miscible IL-API with a solubility increased by around 5 orders of magnitude. Its phase transformations, as crystallization and glass transition, are highly sensitive to the water content, the latter shifting to higher temperatures upon dehydration. By dielectric relaxation spectroscopy the dynamical behavior of anhydrous [C2OHMIM][Ibu] and with 18.5 and 3% of water content (w/w) was probed from well below the calorimetric glass transition (Tg) up to the liquid state. Multiple reorientational dipolar processes were detected which become strongly affected by conductivity and electrode polarization near above Tg. Therefore [C2OHMIM][Ibu] exhibits mixed behavior of a conventional molecular glass former and an ionic conductor being analysed in this work through conductivity, electrical modulus and complex permittivity. The dominant process, σα-process, originates by a coupling between both charge transport and dipolar mechanisms. The structural relaxation times were derived from permittivity analysis and confirmed by temperature modulated differential scanning calorimetry. The temperature dependence of the ß-secondary relaxation is coherent with a Johari-Goldstein (ßJG) process as detected in conventional glass formers.

Confinement effects on the dynamic behavior of poly(D,L-lactic acid) upon incorporation in α-cyclodextrin.

Inclusion complexes (ICs) composed of α-cyclodextrin (α-CD) and poly(D,L-lactic acid) (PDLLA), with 10/24 (IC1) and 15/46 (IC2) (% w/w) of PDLLA incorporated/initial PDLLA weight percentage, were prepared and characterized mainly by dielectric relaxation spectroscopy (DRS). Bulk PDLLA was also analyzed for comparison. DRS was revealed to be a suitable tool to distinguish the dynamical response of the PDLLA regions constrained in between α-CD channels from the fraction incorporated inside channels. While the cooperative α-process undergoes a dramatic depletion shifting to higher temperatures (∼4.5 °C) for the PDLLA interchannels portion, it is suppressed for PDLLA chains inside pores. It was demonstrated that the broad secondary relaxation of bulk PDLLA is the Johari-Goldstein process (ßJG-process). The detection of its analogue in the ICs at higher frequencies, to a greater extent in IC1, is interpreted as a true confinement effect where the dimensions of the α-CD channels interfere with the length scale of the ßJG-process. The limit predicted in the framework of the coupling model, where the α-relaxation transforms in the ßJG-process, seems to be reached in the ICs. Furthermore, it was found that the length scale of the additional γ process only detected in the ICs is inferior to inter- or intrachannel dimensions.

Heavy metal concentrations in edible barnacles exposed to natural contamination.

The giant barnacle Megabalanus azoricus is a popular seafood in the Azores. It is mainly caught in coastal environments and sold for domestic human consumption. This species is a filter feeder and can be used as a biomonitor of trace metal bioavailabilities. To investigate consumption safety, the concentrations of 10 trace metals - As, Cd, Cr, Cu, Mn, Pb, Rb, Se, Sr and Zn - were evaluated in 3 body tissues of M. azoricus from 3 sites on 2 islands. There were no significant differences between the metal loads of the barnacles from the different sites. However, the concentrations of the total trace metal loads revealed significant differences among the tissues (cirrus, muscles and ovaries). The concentrations of some metals in the body were not within the safety levels for consumers, based on the allowable standard levels for crustaceans issued by the European Union and of legislations in several countries. Alarming levels of As and Cd were found. Considering the absence of heavy industry in the region, a non-anthropogenic volcanic source was assumed to be the reason for the observed metal levels. Barnacles, in particular M. azoricus, seem to be useful as bioindicators in this peculiar environment.

Understanding the ion jelly conductivity mechanism.

The properties of the light flexible device, ion jelly, which combines gelatin with an ionic liquid (IL) were recently reported being promising to develop safe and highly conductive electrolytes. This article aims for the understanding of the ion jelly conductive mechanism using dielectric relaxation spectroscopy (DRS) in the frequency range 10(-1)-10(6) Hz; the study was complemented with differential scanning calorimetry (DSC) and pulsed field gradient nuclear magnetic resonance (PFG NMR) spectroscopy. The room temperature ionic liquid 1-butyl-3-methylimmidazolium dicyanamide (BMIMDCA) used as received (1.9% w/w water content) and with 6.6% (w/w) of water content and two ion jellies with two different ratios BMIMDCA/gelatin/water % (w/w), IJ1 (41.1/46.7/12.2) and IJ3 (67.8/25.6/6.6), have been characterized. A glass transition was detected by DSC for all materials allowing for classifying them as glass formers. For the ionic liquid, it was observed that the glass transition temperature decreases with the increase of water content. While in subsequent calorimetric runs crystallization was observed for BMIMDCA with negligible water content, no crystallization was detected for any of the ion jelly materials upon themal cycling. To the dielectric spectra of all tested materials, both dipolar relaxation and conductivity contribute; at the lowest frequencies, electrode and interfacial polarization highly dominate. Conductivity, which manifests much more intensity relative to dipolar reorientations, strongly evidences subdiffusive ion dynamics at high frequencies. From dielectric measures, transport properties as mobility and diffusion coefficients were extracted. Data treatment was carried out in order to deconvolute the average diffusion coefficients estimated from dielectric data in its individual contributions of cations (D(+)) and anions (D(-)). The D(+) values thus obtained for IJ3, the ion jelly with the highest IL/gelatin ratio, cover a large temperature range up to room temperature and revealed excellent agreement with direct measurements from PFG NMR, obeying to the same VFT equation. For BMIMDCA(6.6%water), which has the same water amount as IJ3, the diffusion coefficients were only estimated from DRS measurements over a limited temperature range; however, a single VFT equation describes both DRS and PFG NMR data. Moreover, it was found that the diffusion coefficients and mobility are similar for the ionic liquid and IJ3, which points to a role of both water and gelatin weakening the contact ion pair, facilitating the translational motion of ions and promoting its dissociation; nevertheless, it is conceivable the existence of a critical composition of gelatin that leads to those properties. The VFT temperature dependence observed for the conductivity was found to be determined by a similar dependence of the mobility. Both conductivity and segmental motion revealed to be correlated as inferred by the relatively low values of the decoupling indexes. The obtained results show that ion jelly could be in fact a very promising material to design novel electrolytes for different electrochemical devices, having a performance close to the IL but presenting an additional stability regarding electrical measurements and resistance against crystallization relative to the bulk ionic liquid.

Molecular mobility of nematic E7 confined to molecular sieves with a low filling degree.

The nematic liquid crystalline mixture E7 was confined with similar filling degrees to molecular sieves with constant composition but different pore diameters (from 2.8 to 6.8 nm). Fourier transform infrared analysis proved that the E7 molecules interact via the cyanogroup with the pore walls of the molecular sieves. The molecular dynamics of the system was investigated by broadband dielectric spectroscopy (10(-2)-10(9) Hz) covering a wide temperature range of approximately 200 K from temperatures well above the isotropic-nematic transition down to the glass transition of bulk E7. A variety of relaxation processes is observed including two modes that are located close to the bulk behavior in its temperature dependence. For all confined samples, two relaxation processes, at frequencies lower than the processes observed for the bulk, were detected. At lower temperatures, their relaxation rates have different temperature dependencies whereas at higher temperatures, they seem to collapse into one chart. The temperature dependence of the slowest process (S-process) obeys the Vogel-Fulcher-Tammann law indicating a glassy dynamics of the E7 molecules anchored to the pore surface. The pore size dependence of both the Vogel temperature and fragility revealed a steplike transition around 4 nm pore size, which indicates a transition from a strong to a fragile behavior. The process with a relaxation rate in between the bulklike and the S-process (I-process) shows no dependence on the pore size. The agreement of the I-process with the behavior of a 5CB surface layer adsorbed on nonporous silica leads to the assignment of E7 molecules anchored at the outer surface of the microcrystals of the molecular sieves.

Real-time monitoring of molecular dynamics of ethylene glycol dimethacrylate glass former.

The isothermal cold-crystallization of the glass-former low-molecular-weight compound, ethylene glycol dimethacrylate (EGDMA), was monitored by real-time dielectric relaxation spectroscopy (DRS) and differential scanning calorimetry (DSC). The alpha-relaxation associated with the dynamic glass transition as detected by DRS was followed at different crystallization temperatures, T(cr), nearly above the glass transition temperature, 176 K (1.06 < or = T(cr)/T(g) < or = 1.12). It was found that the alpha-process depletes upon cold-crystallization with no significant changes in either shape or location. At advanced crystallization states, a new relaxation, alpha'-process, evolves that was assigned to the mobility of molecules lying adjacent to crystalline surfaces. From the time evolution of the normalized permittivity, it was possible to get kinetic information that was complemented with the calorimetric data. From DSC measurements that were also carried out under melt-crystallization, an enlarged temperature range was covered (up to T(cr)/T(g) = 1.24), allowing us to draw a diagram of time-temperature crystallization for this system. Dielectric relaxation spectroscopy proved to be a sensitive tool to probe the mobility in the remaining amorphous regions even at high crystallinities.

Confinement and surface effects on the molecular dynamics of a nematic mixture investigated by dielectric relaxation spectroscopy.

Broadband dielectric spectroscopy (10(-2)-10(9) Hz) was employed to investigate the molecular dynamics of the liquid crystalline mixture E7 confined in both untreated and lecithin-treated 20 nm Anopore membranes. Because E7 does not crystallize, it was possible to cover a temperature range of more than 200 K, providing an exhaustive dielectric characterization of a liquid crystal confined to Anopore membranes for the first time. In the nematic state, the tumbling (alpha-) and the delta-relaxation are observed, also under confinement conditions. The analysis of their relative intensities give that the orientation of the E7 molecules is preferentially axial in untreated but opposite radial in lecithin-treated pores. The radial alignment of the liquid crystals in the modified membrane is understood as a tail-to-tail conformation of E7 molecules imposed by the adsorbed lecithin molecules. The relaxation rate of the alpha-process is enhanced for E7 confined in native Anopore compared with the bulk and E7 in treated pores. This is interpreted as resulting from a less dense molecular packing of E7 in the middle of the pore compared to the bulk. In both untreated and treated membranes, the relaxation rate of the delta-process is higher than in the bulk, and the values of the respective Vogel-Fulcher-Tammann temperatures depend on the actual surface treatment. Additionally, a surface process, due to molecular fluctuations of molecules within an adsorbed layer at the pore wall, was detected.

Origin of glassy dynamics in a liquid crystal studied by broadband dielectric and specific heat spectroscopy.

A combination of broadband dielectric (10{-2}Hz-10{9}Hz) and specific heat (10{-3}Hz-2 x 10{3}Hz) spectroscopy is employed to study the molecular dynamics of the glass-forming nematic liquid crystal E7 in a wide temperature range. In the region of the nematic phase the dielectric spectra show two relaxation processes which are expected theoretically: the delta relaxation which corresponds to rotational fluctuations of the molecules around its short axis and the tumbling mode at higher frequencies than the former one. For both processes the temperature dependence of the relaxation rates follows the Vogel-Fulcher-Tammann formula which is characteristic for glassy dynamics. By applying a detailed data analysis, it is shown that close to the glass transition the tumbling mode has a much steeper temperature dependence than the delta process. The former has a Vogel temperature which is by 30K higher than that of the delta relaxation. Specific heat spectroscopy gives one relaxation process in its temperature and frequency dependence which has to be assigned to the alpha relaxation (dynamic glass transition). The unique and detailed comparison of the temperature dependence of the dielectric and the thermal relaxation rates delivers unambiguously that the dielectric tumbling mode has to be related to the dynamic glass transition.

Development of a decision support system for diagnosis and grading of brain tumours using in vivo magnetic resonance single voxel spectra.

A computer-based decision support system to assist radiologists in diagnosing and grading brain tumours has been developed by the multi-centre INTERPRET project. Spectra from a database of 1H single-voxel spectra of different types of brain tumours, acquired in vivo from 334 patients at four different centres, are clustered according to their pathology, using automated pattern recognition techniques and the results are presented as a two-dimensional scatterplot using an intuitive graphical user interface (GUI). Formal quality control procedures were performed to standardize the performance of the instruments and check each spectrum, and teams of expert neuroradiologists, neurosurgeons, neurologists and neuropathologists clinically validated each case. The prototype decision support system (DSS) successfully classified 89% of the cases in an independent test set of 91 cases of the most frequent tumour types (meningiomas, low-grade gliomas and high-grade malignant tumours--glioblastomas and metastases). It also helps to resolve diagnostic difficulty in borderline cases. When the prototype was tested by radiologists and other clinicians it was favourably received. Results of the preliminary clinical analysis of the added value of using the DSS for brain tumour diagnosis with MRS showed a small but significant improvement over MRI used alone. In the comparison of individual pathologies, PNETs were significantly better diagnosed with the DSS than with MRI alone.

Dielectric characterization of neutralized and nonneutralized chitosan upon drying.

Isothermal dielectric loss spectra of neutralized and nonneutralized chitosan were acquired in successive runs from -130 degrees C up to increasing final temperatures, in a frequency range between 20 Hz and 1 MHz. Essentially, three relaxation processes were detected in the temperature range covered: (i) a beta-wet process, detected when the sample has a higher water content that vanishes after heating to 150 degrees C; (ii) a beta process, which is located at temperatures below 0 degrees C, becoming better defined and maintaining its location after annealing at 150 degrees C independently of the protonation state of the amino side group; and (iii) a sigma process that deviates to higher temperatures with drying, being more mobile in the nonneutralized form. Moreover, in dried neutralized chitosan, a fourth process was detected in the low frequency side of the secondary beta process that diminishes after annealing. Whether this process is a distinct relaxation of the dried polymer or a deviated beta-wet process due to the loss of water residues achieved by annealing is not straightforward. Only beta and sigma processes persist after annealing at 150 degrees C. The changes in molecular mobility upon drying of these two relaxation processes were evaluated.

[Central chemoreceptors and sudden infant death syndrome]. / Quimiorreceptores centrales y síndrome de muerte súbita del lactante.

INTRODUCTION: Carbon dioxide partial pressure and pH in the extracellular compartment are the most powerful signals regulating respiration. Central chemoreceptors (QC) undergo the stimulating effect of CO2 and pH upon respiration. AIMS: This review tries to provide an actual envision of the progress in the knowledgement on central chemoreception. It also tries to highlight the importance of the alterations in the chemoreception mechanism as a cause of sudden infant death syndrome (SIDS). DEVELOPMENT: Central chemoreceptors respond to acid-base imbalance acting on neurons that give rise to the central breathing pattern and have the ability to change the respiratory rate, which is normally needed to restore the normal values of acid-base status. QC are widely distributed in the brain stem, however QC neurons in the ventral surface of the medulla like to be the main relays for ventilatory responses after acid-base stimulation. CONCLUSIONS: It has been shown that QC are sensitive to pH and CO2 as in vivo as in vitro conditions, most of them being serotonin immunopositive, a neurotransmitter with known effects on breathing pattern. By other side, alterations of central chemoreception have been associated to pathologies like congenital hypoventilatory syndrome or SIDS. Interestingly, the post mortem exams of the brain of infants dead because these syndromes have showed anomalies of serotonergic receptor located in regions containing QC neurons and in others related with cardiorespiratory integration.

Molecular motions in chitosan studied by dielectric relaxation spectroscopy.

Neutralized and nonneutralized chitosan films subject to different thermal treatments were studied by dielectric relaxation spectroscopy from -130 to +150 degrees C in the frequency range between 20 Hz and 1 MHz. Two main relaxation processes, both arrhenian type, were detected: process I at temperatures below 0 degrees C with a mean activation energy of 49 +/- 1 kJ mol(-1), which has the characteristics of a secondary relaxation process related with local chain dynamics, and process II observable at higher temperatures with an activation energy of 94 +/- 2 kJ mol(-1), correlated with dc conductivity, which is found in dried polysaccharides systems. Process I is always observed in neutralized chitosan, but it is strongly depleted in the wet nonneutralized form. Although the location of process I is independent of NH2/NH3+ side group, process II deviates to higher temperatures with dryness in both chitosan forms, being located at lower temperatures in nonneutralized chitosan.

Evolución postquirúrgica de pacientes con hiperplasia prostática benigna / Post-surgical evolution of patients with benign prostate hyperplasia

Se realizó un estudio retrospectivo en 45 pacientes ingresados en el Hospital Dr. Salvador Gautier, Santo Domingo, en el período enero-junio 1992, con el objetivo de determinar la evolución post-quirúrgica de la hiperplasia prostática benigna. En dicho estudio se observó que la edad más afectada corresponde a los pacientes entre 71-80 años, con 16 casos, se presentó la retención urinaria en 30 pacientes (66.7//) seguido por nicturia en 23 pacientes. La tecnología quirúrgica más usada fue la transvesical en 39 pacientes (86.7//). Los reportes anatomopatológicos reportaron hiperplasia en 18 pacientes (40//); hiperplasia fibroadeno-matosa benigna de la próstata, 14 pacientes (31.1//); otros reportes correspondieron a hiperplasia e hipertrofia fibromuscular con prostatitis crónica e hiperplasia-hipertrófica nodular con prostatitis crónica con 4 (8.9//). Las complicaciones presentadas por las fistula vesicocutánea, infecciones y disuria con 5 pacientes (11.1//), seguido en orden de frecuencia por dificultad para orinar, hematuria con 3 pacientes (6.7//) seguido de otros como epidimitis, dolor lumbar, chorro fino, laceración uretral, etc. próstata, hiperplasia benigna, evolución post-quirúrgica, cirugía, urología

A case of silicosis associated with Crohn's disease. Diagnostic and pathogenetic considerations.

A case of silicosis associated with Crohn's disease is reported. Symptoms, radiological and endoscopical findings suggested Crohn's disease in a man, who had worked as ceramist and in whom silicosis was diagnosed four years earlier. The authors, after presenting the clinical and diagnostic features of the patient, discuss the similarity of some pathogenetic features of the two diseases. They hypothesize a common pathogenetic immunological defect in the two diseases, probably caused by inhalation of silica.

Gastric lymphoma: diagnosis and follow-up of chemotherapy-induced changes using real-time ultrasonography: a report of three cases.

Three cases of secondary gastric lymphoma are presented in which diagnosis was suggested by ultrasound (US) and confirmed by endoscopy and microscopical examination. Three different US patterns are illustrated and compared with endoscopy. US findings paralleled endoscopy during follow-up under antiblastic treatment: both improvement and lack of change in the gastric lesions were reliably predicted by US.