Self-Healing Polymeric Soft Actuators.

Natural evolution has provided multicellular organisms with sophisticated functionalities and repair mechanisms for surviving and preserve their functions after an injury and/or infection. In this context, biological systems have inspired material scientists over decades to design and fabricate both self-healing polymeric materials and soft actuators with remarkable performance. The latter are capable of modifying their shape in response to environmental changes, such as temperature, pH, light, electrical/magnetic field, chemical additives, etc. In this review, we focus on the fusion of both types of materials, affording new systems with the potential to revolutionize almost every aspect of our modern life, from healthcare to environmental remediation and energy. The integration of stimuli-triggered self-healing properties into polymeric soft actuators endow environmental friendliness, cost-saving, enhanced safety, and lifespan of functional materials. We discuss the details of the most remarkable examples of self-healing soft actuators that display a macroscopic movement under specific stimuli. The discussion includes key experimental data, potential limitations, and mechanistic insights. Finally, we include a general table providing at first glance information about the nature of the external stimuli, conditions for self-healing and actuation, key information about the driving forces behind both phenomena, and the most important features of the achieved movement.

Lignin-Based Catalysts for C-C Bond-Forming Reactions.

Carbon-carbon (C-C) bond formation is the key reaction in organic synthesis to construct the carbon framework of organic molecules. The continuous shift of science and technology toward eco-friendly and sustainable resources and processes has stimulated the development of catalytic processes for C-C bond formation based on the use of renewable resources. In this context, and among other biopolymer-based materials, lignin has attracted scientific attention in the field of catalysis during the last decade, either through its acid form or as a support for metal ions and metal nanoparticles that drive the catalytic activity. Its heterogeneous nature, as well as its facile preparation and low cost, provide competitive advantages over other homogeneous catalysts. In this review, we have summarized a variety of C-C formation reactions, such as condensations, Michael additions of indoles, and Pd-mediated cross-coupling reactions that were successfully carried out in the presence of lignin-based catalysts. These examples also involve the successful recovery and reuse of the catalyst after the reaction.

Evaluation of electrical nerve stimulation to confirm sacrococcygeal epidural needle placement in dogs.

OBJECTIVES: To evaluate the use of 0.7 mA as a fixed electrical current to indicate epidural needle placement and to confirm that 0.7 mA is greater than the upper limit of the minimal electrical threshold (MET) for sacrococcygeal epidural needle placement in dogs. STUDY DESIGN: Prospective clinical study. ANIMALS: A group of 20 client-owned dogs. METHODS: During general anesthesia and with standard monitoring, the presence of the patellar reflex was confirmed in all dogs. An insulated needle was inserted through the sacrococcygeal intervertebral junction, and absence of tail movement was confirmed when a fixed electrical current of 0.7 mA was applied. Then, the needle was further advanced toward the epidural space until the expected motor response was obtained - the nerve stimulation test (NST). The NST was considered positive when a motor response of the muscles of the tail was elicited but not the perineal muscles, whereas it was considered negative when no movement of the tail was evoked. The electrical current was turned to 0 mA and then increased by 0.01 mA increments until tail movement was evoked; this was recorded as the MET. In the positive NST cases, 0.05 mL cm-1 occipitococcygeal length of 2% lidocaine or 0.25-0.5% bupivacaine was administered. Epidural blockade was confirmed by the loss of patellar reflex. Descriptive statistics were used to present data. RESULTS: Sacrococcygeal epidural needle placement, corroborated by loss of the patellar reflex, was correctly predicted in 89.5% (95% confidence interval, 68.6-97.1%) of the cases. The MET was 0.22 mA (0.11-0.36). CONCLUSIONS AND CLINICAL RELEVANCE: A current of 0.7 mA is approximately twice the upper limit of the MET for epidural placement. Therefore, this study demonstrates, with a success rate of 89.5%, the adequacy of using 0.7 mA as the fixed electrical current to detect sacrococcygeal epidural needle placement in dogs.

Superior performance of 18F-fluorocholine digital PET/CT in the detection of parathyroid adenomas.

OBJECTIVE: To compare detectability of hyperfunctioning parathyroid tissue (HPT) by digital and analog 18F-fluorocholine PET/CT in patients with primary hyperparathyroidism and negative/inconclusive 99mTc-MIBI scintigraphy-SPECT/CT. MATERIALS AND METHODS: Thirty-three patients with primary hyperparathyroidism and negative/inconclusive 99mTc-MIBI scintigraphy-SPECT/CT were prospectively included. All patients accepted to be scanned by digital and analog PET/CT in the same imaging session after a single injection of 18F-fluorocholine. Three nuclear medicine physicians evaluated the digital and analog PET/CT datasets to assess the detection rate of HPT. Maximum standard uptake values (SUVmax) of HPT and locoregional lymph nodes were measured in both systems. RESULTS: HPT was detected in 30/33 patients by the digital system, whereas it was detected in 22/33 patients by the analog system (p < 0.01). Moreover, in 21 of these 33 patients, both systems detected one focal 18F-fluorocholine uptake, and in one patient the digital system detected two foci. Histopathology demonstrated HPT in 32 patients and it was inconclusive in one patient. The digital PET/CT detected HPT in 29 of the 32 patients, and the analog system in 22 of the 32 (p < 0.01). All HPT suspected lesions resected and detected only by the digital system (n = 8) were < 10 mm (7.5 ± 1.3 mm), while those detected by both systems (n = 22) were > 10 mm (13 ± 3.8 mm). SUVmax of HPT lesions was significantly higher than SUVmax of locoregional lymph node independently of the PET/CT system used (4.5 ± 1.9 vs. 2.9 ± 1.3, p < 0.0001). CONCLUSIONS: Digital PET/CT offers superior performance over analog system in patients with suspected HPT and previous negative/inconclusive imaging examinations, particularly in sub-centimeter lesions. SUVmax can help in the differentiation between HTP and locoregional lymph nodes.

Correction to: Superior performance of 18F-fluorocholine digital PET/CT in the detection of parathyroid adenomas.

The correct administered activity of 18F-FCH is 0.1-0.14 mCi/Kg, which is equivalent to 3.7-5.2 MBq/kg.

Effects of oxygen on post-surgical infections during an individualised perioperative open-lung ventilatory strategy: a randomised controlled trial.

BACKGROUND: We aimed to examine whether using a high fraction of inspired oxygen (FIO2) in the context of an individualised intra- and postoperative open-lung ventilation approach could decrease surgical site infection (SSI) in patients scheduled for abdominal surgery. METHODS: We performed a multicentre, randomised controlled clinical trial in a network of 21 university hospitals from June 6, 2017 to July 19, 2018. Patients undergoing abdominal surgery were randomly assigned to receive a high (0.80) or conventional (0.3) FIO2 during the intraoperative period and during the first 3 postoperative hours. All patients were mechanically ventilated with an open-lung strategy, which included recruitment manoeuvres and individualised positive end-expiratory pressure for the best respiratory-system compliance, and individualised continuous postoperative airway pressure for adequate peripheral oxyhaemoglobin saturation. The primary outcome was the prevalence of SSI within the first 7 postoperative days. The secondary outcomes were composites of systemic complications, length of intensive care and hospital stay, and 6-month mortality. RESULTS: We enrolled 740 subjects: 371 in the high FIO2 group and 369 in the low FIO2 group. Data from 717 subjects were available for final analysis. The rate of SSI during the first postoperative week did not differ between high (8.9%) and low (9.4%) FIO2 groups (relative risk [RR]: 0.94; 95% confidence interval [CI]: 0.59-1.50; P=0.90]). Secondary outcomes, such as atelectasis (7.7% vs 9.8%; RR: 0.77; 95% CI: 0.48-1.25; P=0.38) and myocardial ischaemia (0.6% [n=2] vs 0% [n=0]; P=0.47) did not differ between groups. CONCLUSIONS: An oxygenation strategy using high FIO2 compared with conventional FIO2 did not reduce postoperative SSIs in abdominal surgery. No differences in secondary outcomes or adverse events were found. CLINICAL TRIAL REGISTRATION: NCT02776046.

Optimization of the Synthesis of Glycerol Derived Monoethers from Glycidol by Means of Heterogeneous Acid Catalysis.

We present an efficient and green methodology for the synthesis of glycerol monoethers, starting from glycidol and different alcohols, by means of heterogeneous acid catalysis. A scope of Brønsted and Lewis acid catalysts were applied to the benchmark reaction of glycidol and methanol. The selected catalysts were cationic exchangers, such as Nafion NR50, Dowex 50WX2, Amberlyst 15 and K10-Montmorillonite, both in their protonic form and exchanged with Al(III), Zn(II) and Fe(III). Thus, total conversions were reached in short times by using 1 and 5% mol catalyst loading and room temperature, without the need for excess glycidol or the presence of a solvent. Finally, these conditions and the best catalysts were successfully applied to the reaction of glycidol with several alcohols such as butanol or isopropanol.

Pancreatic stent insertion after an unintentional guidewire cannulation of the pancreatic duct during ERCP.

INTRODUCTION: the guidewire (GW) may enter the pancreatic duct during common bile duct (CBD) cannulation attempts in endoscopic retrograde cholangiopancreatography (ERCP). After GW passage into the pancreas, the most effective maneuver for CBD cannulation and pancreatitis prevention has not been determined. AIM: to study CBD cannulation and post-ERCP pancreatitis rates when a pancreatic stent is inserted after an unintentional GW cannulation of the pancreatic duct. MATERIAL AND METHODS: a retrospective analysis of patients undergoing ERCP for biliary drainage that were included prospectively into a database. After unintentional GW cannulation of the pancreatic duct, a straight 5-Fr and 4-cm long plastic stent was inserted. The stents had no internal flaps to facilitate expulsion. CBD cannulation attempts were made above the stent. A pancreatic sphincterotomy was performed in patients older than 60 years before stent insertion. RESULTS: a total of 46 pancreatic stents were inserted during 154 ERCP (29.8%) procedures. In the stent group, CBD cannulation was accomplished in 44/46 (95.6%) subjects. A total of 21/46 (45.6%) pancreatic sphincterotomies were performed. Only 1/46 (2.17%) mild pancreatitis cases were observed and most stents were spontaneously expelled. CONCLUSIONS: in this study, the CBD was eventually reached with the insertion of a plastic pancreatic stent after an unintentional GW passage into the pancreatic duct while attempting a CBD cannulation. No adverse events were observed following pancreatic stent insertion.

Comparative ecotoxicology study of two neoteric solvents: Imidazolium ionic liquid vs. glycerol derivative.

In this study we have compared the acute ecotoxicity of two solvents, with very different structure and origin, but sharing many physical-chemical properties, so they can be used for similar purposes; a well-known ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) and a solvent partially derived from biomass, 3-bis(2,2,2-trifluoroethoxy)propan-2-ol (BTFIP). We have used three biomodels (Vibrio fischeri, Daphnia magna and Danio rerio) and performed the comparison applying the Environmental, Health and Safety (EHS) hazard assessment. According to the results, ecotoxicity of [BMIM][PF6] and BTFIP is quite similar in the simplest model Vibrio fischeri, while in Daphnia magna [BMIM][PF6] is clearly more toxic. However, in Danio rerio, toxicity of these chemicals is again quite similar and both can be classified as "nontoxic". The higher index value of [BMIM][PF6] in water mediate effect in the EHS assessment indicates that this ionic liquid is more dangerous than BTFIP, although accumulation and degradation properties have not been taken into account. Further studies will be necessary to ascertain these conclusions.

Dual electro-/pH-responsive nanoparticle/hydrogel system for controlled delivery of anticancer peptide.

An electro-chemo-responsive carrier has been engineered for the controlled release of a highly hydrophilic anticancer peptide, CR(NMe)EKA (Cys-Arg- N-methyl-Glu-Lys-Ala). Remotely controlled on demand release of CR(NMe)EKA, loaded in electro-responsive poly(3,4-ethylenedioxythiophene) (PEDOT) nanoparticles, has been achieved by applying electrical stimuli consisting of constant positive (+0.50 V) or negative voltages (-0.50 V) at pre-defined time intervals. In addition, after loading CR(NMe)EKA/PEDOT nanoparticles into an injectable pH responsive hydrogel formed by phenylboronic acid grafted to chitosan (PBA-CS), the efficiency of the controlled peptide release has increased approximately by a factor of 2.6. The hydration ratio of such hydrogel is significantly lower in acidic environments than in neutral and basic media, which has been attributed to the dissociation of the boronate bonds between polymer chains. Hence, the electro-controlled peptide release from PBA-CS/CR(NMe)EKA/PEDOT hydrogels, in the acidic environment of tumors, combines the effects of the oxidation and reduction of PEDOT chains on the interactions with the peptide and the carrier, with the peptide concentration gradient at the interface between the collapsed hydrogel and the release medium. Furthermore, the peptide released by electro-stimulation preserved its bioactivity assessed by promoting human prostate cancer cells death. Overall, this work is a promising attempt to develop a carrier platform for small hydrophilic anticancer peptides, which delivery rationale is synergistically regulated by the electrical and pH responsiveness of the carrier.

Fully covered self-expanding metal stents in the management of difficult common bile duct stones.

BACKGROUND AND OBJECTIVES: plastic biliary stents are often used after an ERCP session without complete common bile duct stones (CBDS) extraction. Sometimes, the volume of biliary drainage with these stents may be insufficient. We present our experience with the use of fully covered self-expanding metal stents (FCSEMS) in the setting of incomplete CBDS extraction. PATIENTS AND METHODS: after an ERCP session with difficult CBDS not completely removed, biliary FCSEMS (Wallflex) were inserted in some patients when it was deemed that biliary sphincterotomy and a single plastic stent would not provide an adequate drainage. RESULTS: a retrospective study was performed. Biliary FCSEMS were inserted in 29 patients, mean age 81 years. CBDS could not be extracted through a biliary sphincterotomy due to its large size (n = 18) or because of the presence of inflammatory distal strictures (n = 11). The greatest biliary drainage with shortest ERCP time was considered mandatory due to clinical instability of patients and/or poor tolerance to conscious sedation administered by the endoscopist. Successful biliary drainage was obtained in all cases. FCSEMS were removed after a median of 199.5 days in 16 patients with a complete CBDS extraction in 15 (93.7%). FCSEMS were not removed in the remaining 13 patients due to their clinical condition, and a wait-and-see strategy was undertaken. CONCLUSIONS: in selected cases, utilization of removable FCSEMS can be a good option for a quick and adequate biliary drainage in the setting of difficult CBDS. Because of the higher cost of these stents its use needs to be individualized.

"Geographical distribution of risk genotypes in pediatric patients with celiac disease in Spain".

Celiac disease is strongly associated with HLA DQ, specifically with haplotypes. DRB1*03-DQA1*05:01/DQB1*02:01 (DQ2.5),DRB1*07-DQA1*02:01/DQB1*02:02 (DQ2.2), DRB1*11-DQA1*05:05/DQB1*03:01 (DQ7.5), and DRB1*04-DQA1*03:01/DQB1*03:02 (DQ8). The distribution of these risk haplotypes in patients with celiac disease is different in the geographical areas investigated. A high frequency of DRB1*07- DQA1*02:01/DQB1*02:02 (DQ2.2) and DRB1*11-DQA1*05:05/DQB1*03:01 (DQ7.5), has been described in Southern Europe. We analyzed 2102 confirmed CD cases with information on both DQB1* alelles and their distribution by geographical area in Spain. According to the presence of this haplotype in one or two chromosomes, the genotype is classified in: DQ2 homozygous, DQ2 heterozygous (cis or trans), DQ8 homozygous, DQ8/DQ2.5, DQ 2.2 homozygous and genotype known as "half DQ2". Two different patterns of risks related to CD were identified. In the Basque Country and Navarre, the Mediterranean Area (Aragon, Catalonia, Valencia, Balearic Islands, and Murcia), the South of Spain (Andalucía and Extremadura), and the Canary Islands, higher frequency of DQ2.5 trans, and more than 80% of DQ2.5/DQ2.2 homozygosis were described. The Cantabrian Coast (Cantabria, Asturias, and Galicia) and Central Areas (Castilla-León and Castilla-La Mancha) showed a higher percentage of DQ2.5/DQ2.5 homozygosis and a lower DQ2.5 in trans frequency, as in Northern Europe. Madrid has an intermediate model between the two described above. 17 cases (0.8%) did not carry any CD risk haplotypes.

DFT studies on cobalt-catalyzed cyclotrimerization reactions: the mechanism and origin of reaction improvement under microwave irradiation.

A DFT computational mechanistic study of the [2+2+2] cyclotrimerization of a diyne with benzonitrile, catalyzed by a cobalt complex, has been carried out. Three alternative catalytic cycles have been examined together with the precatalytic step (responsible for the induction period). The favored mechanism takes place by means of an intramolecular metal-assisted [4+2] cycloaddition. The beneficial role of microwave activation has been studied. It is concluded that microwave irradiation can decrease the catalytic induction period through thermal effects and can also increase the triplet lifetime and promote the reaction, thus improving the final yield.

[Co-expression of estrogen receptors and Her2/neu in breast cancer. Neoadjuvant chemotherapy sentinel lymph node and hormonotherapy]. / Cancer de mama con Her-2-neu y receptores hormonales positivos. Quimioterapia neoadyuvante, biopsia de ganglio centinela y tratamiento hormonal.

Neoadjuvant chemotherapy is an interesting option in the therapy of some breast cancer cases. Cases in which the timing for sentinel lymph node biopsy is controversial. Co-expression of estrogen receptors and Her2/neu (c-erbB-2) in breast cancer may imply hormone resistance, especially to tamoxifen. We present a clinic case with co-expression of estrogen receptors and Her2/neu that was treated with neoadjuvant chemotherapy and previous sentinel lymph node biopsy followed by breasttumorectomy with axillar lymphadenectomy, radiotherapy and hormonotherapy with letrozol, geserelina and trastuzumab. A good treatment response was found.

[A prospective, multicentre study on the activity of general and digestive surgery residents based on the use of the computerised logbook]. / Estudio prospectivo, multicéntrico sobre la actividad de los residentes de cirugía general y del aparato digestivo en España a través del libro informático del residente.

INTRODUCTION: There are no quantified data on the real activity carried out by residents during the 5 years of training in the specialty of general and digestive surgery (GGS) in Spain. There are also limited data on programs in other surgical specialities, and in other countries. The aim of the study is to estimate the mean overall surgical activity by specific skill areas and by the level of complexity of the Spanish program in the specialty of GGS. PATIENTS AND METHOD: A prospective, observational, multicentre study was performed on the activity of GGS residents in Spain using the Resident Computerised Logbook of the Spanish Surgeons Association (LIR-AEC). Each of the residents registered their own activity supervised by their tutor. The sample period was 6 months. The medians of the annual activity and the period of residency were calculated from the results. RESULTS: Surgical activity: during the residency, it was estimated that that they attended 1,325 operations, 654 (49%) as lead surgeon. Health care activity: the mean number of times on-call was 5.2±1.8 per month. Activity in outpatient clinics was 548 first visits, and almost double for second visits. Scientific activity: the total number of courses and conferences attended was 34. The estimated mean number of presentations at conferences was 14, with 3 publications. CONCLUSIONS: LIR-AEC is a suitable tool to verify activity in the Spanish GGS Program. These results may be useful for comparing with training programs in other countries and in other surgical specialties.

Proximal Abduction Ulnar Osteotomy (PAUL): Short- and Long-Term Evaluation in Dogs Presenting Medial Compartment Disease.

The aim of the study is to report the results obtained from performing a Proximal Abduction Ulnar Osteotomy (PAUL) technique in a cohort of dogs with medial compartment disease with short- and long-term follow-up, assessing the perception of the owners and describing the long-term complications associated with the technique. This is a clinical prospective study, including dogs diagnosed with medial compartment disease treated with elbow arthroscopy and PAUL between 2013 and 2020. Long-term follow-up data and postoperative complications were registered, and a questionnaire adapted from Fitzpatrick et al. 2009 was collected from owners. Thirty-three elbows in 26 dogs were included. The duration of follow-up ranged from 4 to 61 months (median: 24.76 months). At the end of the study, 73.1% of the owners reported excellent satisfaction and 74.1% of the owners would repeat the surgery in the same circumstances. The owner questionnaire showed a greater capacity to walk and run, without lameness and pain, and climb up and down stairs a year after surgery, being constant at the end of the study. Major postoperative complications were documented in 4/33 elbows (12.12%), including delayed union, implant failure, and osteophytosis of the medial aspect of the coronoid process. In conclusion, elbow arthroscopy and the PAUL technique achieved an evident improvement in the quality of life of patients with great satisfaction for most of the owners.

Standard criteria versus Rosemont classification for EUS-diagnosis of chronic pancreatitis.

AIM: to study the possible differences in the final diagnosis of chronic pancreatitis by using standard classification described by Wiersema et al. and the new classification proposed recently by Rosemont. MATERIAL AND METHODS: forty-seven patients with the diagnosis of chronic pancreatitis were included in this study. The parenchymal and ductal criteria were studied, the patients were divided in two groups for Wiersema criteria: < 4 criteria, non-diagnostic for chronic pancreatitis and ≥ 4 criteria, diagnosis of chronic pancreatitis. The same patients were divided in four groups according to Rosemont classification: normal pancreas, indeterminate, suggestive and consistent with chronic pancreatitis. We analyzed these data with Chisquare test reported with 95% confidence intervals (CI). RESULTS: in patients with chronic pancreatitis the most frequent criteria observed were lobularity in 66% of cases and pancreatic duct dilatation and calcifications in 57.4% of cases each. We found a significant statistical association between the results of both classifications (p < 0.05). The highest association is found in patients with more than 4 standard criteria and definitive diagnostic of chronic pancreatitis according to Rosemont classification. In patients who have less than 4 standard criteria the diagnosis is suggestive of chronic pancreatitis by using the Rosemont classification in 27.66% (p < 0.05). CONCLUSION: these results show that no significant statistical differences are found for patients with > 4 criteria diagnosis by standard criteria. But 27.66% patients with less than 4 standard criteria would be suggestive according to Rosemont classification (p < 0.05). Hence, the new classification would be useful in patients with high suspicion of chronic pancreatitis with < 4 standard criteria but with more significance such as parenchymal lithiasis, lobularity or ductal calcifications.

Thermal and Photocatalytic Performance of Unsaturated Polyester Resins Modified with TiO2 Nanoparticles as Panel Bodies for Vehicles.

The transport sector is the fastest growing contributor to climate emissions and experiences the highest growth in energy use. This study explores the use of TiO2 nanoparticles for obtaining photocatalytic nanocomposites with improved infrared reflectance properties. The nanocomposites were prepared by dispersing 0-20 wt% of TiO2 nanoparticles in an unsaturated polyester resin. The effect of TiO2 on the curing kinetics was studied by differential scanning calorimetry, showing a significant delay of the curing reactions. The thermal reflectance of the modified resins was characterized by UV-Vis-NIR spectrophotometry, measuring total solar reflectance (TSR). The TiO2 greatly increased the TSR of the resin, due to the reflectance properties of the nanoparticles and the change in color of the modified resin. These nanocomposites reflect a significant part of near-infrared radiation, which can contribute to a reduction of the use of heating, ventilation, and air conditioning. Moreover, the photocatalytic effect of the TiO2 modified nanocomposites was studied by monitoring the degradation of an organic model contaminant in an aqueous medium under UV light, and the reusability of the nanocomposites was studied with 5 cycles. The developed nanocomposites are proposed as a solution for reducing global warming and pollutant emissions.