Health-related quality of life and associated risk factors in patients with Multiple Osteochondromas: a cross-sectional study.

PURPOSE: To evaluate the health-related quality of life and associated risk factors for Multiple Osteochondromas patients. METHODS: A cross-sectional, observational study was conducted from May to December 2022 during the routine visit to the referral center for rare skeletal disorders. All patients with Multiple Osteochondromas aged ≥ 3 years were included. EuroQol 5-dimension questionnaires, and demographic, clinical, and surgical history data were collected. Descriptive statistics, Fisher's exact test, One-sample t-test, Spearman's correlation, and multiple linear and logistic regression were performed to analyze the data. Results are reported following STROBE guidelines. RESULTS: A total of 128 patients were included in the study, with a mean age of 14 [SD, 10] years. The mean EQ-5D Index Value was 0.863 [SD, 0.200] and the EQ-VAS was 84 [SD, 19] with a positive correlation between two scores [r = 0.541, p < 0.001]. Patients frequently referred problems in pain/discomfort [78.8%], anxiety/depression [50%], and usual activities [38.8%] dimensions. Increasing age was the common risk factor for health-related quality of life [p < 0.000], as well as Index Value and VAS scores were significantly lower in surgical patients [p = 0.001 and p < 0.001, respectively]. CONCLUSION: Increasing age and surgical procedures were found highly associated with reduced health-related quality of life in Multiple Osteochondromas patients. Our findings provide relevant information to support the establishment of patient-centered healthcare pathways and pave the way for further research into medical and non-medical therapeutic strategies for these patients.

Residual elbow instability in children with posterior or postero-lateral elbow dislocation.

The purpose of this study is to evaluate the incidence and the severity of residual elbow instability in children treated for posterior (PED) or postero-lateral (PLED) elbow dislocation. This retrospective study included all children younger than 14 years of age with a confirmed diagnosis of acute post-traumatic elbow dislocation (ED). Subjective data such as perceived pain, stiffness and impact of daily activities, and objective data such as skin lesions, surgical-site infections, and range of motion were recorded. All patients underwent the milking test, the chair sign test (CST) and the Drawer test (DT). The functional status has been rated according to the Mayo Elbow Performance Score (MEPS) and the Roberts criteria (RC). Radiographs of the injured arm were performed at the last follow-up visit to evaluate axial alignment, growth disturbances, osteoarthrosis, heterotopic calcifications, and the presence of loose intra-articular bodies. Nineteen patients with a mean age of 9 years and 5 months at the time of injury were available for review. Six patients had PED (31.6%) and 13 PLED (68.4%); in five cases (26.3%) the dislocation was simple and in 14 cases (73.7%) it was complex. None of the patients complained of subjective symptoms of elbow instability, although 2 patients had positive CST, and one of them also had positive milking test. RC and MEPS ranged from good to excellent in all patients. Clinical examination with multiple stability tests is important to detect residual elbow instability in children treated for ED as functional scores alone may underestimate the clinical picture.

Osteogenesis imperfecta: a cross-sectional study of skeletal and extraskeletal features in a large cohort of Italian patients.

Introduction: The present study aims to describe a large cohort of Italian patients affected by osteogenesis imperfecta, providing a picture of the clinical bony and non-bony features and the molecular background to improve knowledge of the disease to inform appropriate management in clinical practice. Methods: A total of 568 subjects (from 446 unrelated Italian families) affected by osteogenesis imperfecta who received outpatient care at Istituto Ortopedico Rizzoli from 2006 to 2021 were considered in the present study. Results: Skeletal and extraskeletal features were analyzed showing a lower height (mean z-scores equal to -1.54 for male patients and -1.47 for female patients) compared with the general Italian population. Half of the patient population showed one or more deformities, and most of the patients had suffered a relatively low number of fractures (<10). An alteration in the sclera color was identified in 447 patients. Similarly, several extraskeletal features, like deafness, dental abnormalities, and cardiac problems, were investigated. Additionally, inheritance and genetic background were evaluated, showing that most of the patients have a positive family history and the majority of pathogenic variants detected were on collagen genes, as per literature. Conclusion: This study supports the definition of a clear picture of the heterogeneous clinical manifestations leading to variable severity in terms of skeletal and extra-skeletal traits and of the genetic background of an Italian population of osteogenesis imperfecta patients. In this perspective, this clearly highlights the crucial role of standardized and structured collection of high-quality data in disease registries particularly in rare disease scenarios, helping clinicians in disease monitoring and follow-up to improve clinical practice.

Virtual Surgical Planning, 3D-Printing and Customized Bone Allograft for Acute Correction of Severe Genu Varum in Children.

Complex deformities of lower limbs are frequent in children with genetic or metabolic skeletal disorders. Early correction is frequently required, but it is technically difficult and burdened by complications and recurrence. Herein, we described the case of a 7-year-old girl affected by severe bilateral genu varum due to spondyloepiphyseal dysplasia. The patient was treated by patient-specific osteotomies and customized structural wedge allograft using Virtual Surgical Planning (VSP) and 3D-printed patient-specific instrumentation (PSI). The entire process was performed through an in-hospital 3D-printing Point-of-Care (POC). VSP and 3D-printing applied to pediatric orthopedic surgery may allow personalization of corrective osteotomies and customization of structural allografts by using low-cost in-hospital POC. However, optimal and definitive alignment is rarely achieved in such severe deformities in growing skeleton through a single operation.

Microplastic contamination of supraglacial debris differs among glaciers with different anthropic pressures.

Microplastic (MP) contamination is ubiquitous and widespread in terrestrial and aquatic ecosystems, including remote areas. However, information on the presence and distribution of MPs in high-mountain ecosystems, including glaciers, is still limited. The present study aimed at investigating presence, spatial distribution, and patterns of contamination of MPs on three glaciers of the Ortles-Cevedale massif (Central Alps, Northern Italy) with different anthropic pressures, i.e., the Forni, Cedec and Ebenferner-Vedretta Piana glaciers. Samples of supraglacial debris were randomly collected from the glaciers and MPs were isolated. The mean amount (±SE) of MPs measured in debris from Forni, Cedec and Ebenferner-Vedretta Piana glaciers was 0.033 ± 0.007, 0.025 ± 0.009, and 0.265 ± 0.027 MPs g-1 dry weight, respectively. The level and pattern of MP contamination from the Ebenferner-Vedretta Piana glacier were significantly different from those of the other glaciers. No significant spatial gradient in MP distribution along the ablation areas of the glaciers was observed, suggesting that MPs do not accumulate toward the glacier snout. Our results confirmed that local contamination can represent a relevant source of MPs in glacier ecosystems experiencing high anthropic pressure, while long-range transport can be the main source on other glaciers.

The hidden cost of following currents: Microplastic ingestion in a planktivorous seabird.

Microplastics are increasingly pervasive pollutants, particularly abundant in the neuston where they drift with currents. We assessed dietary microplastic ingestion in the Mediterranean storm petrel (Hydrobates pelagicus melitensis), a small pelagic seabird that forages on plankton and inhabit the Mediterranean sea, one of the most polluted seas worldwide. We collected spontaneous regurgitates from 30 chick-rearing individuals and used GPS tracking data from 7 additional individuals to locate foraging areas. Birds foraged in pelagic areas characterized by water stirring and mixing, and regurgitates from 14 individuals (i.e. 45 %) contained microplastics. Fibers were the dominant shape (56 %), with polyester, polyethylene and nylon being the most frequent polymers. Our findings highlight the potential sensitivity of this species of conservation interest to plastic pollution and suggest that storm petrel regurgitates can be a valuable matrix to investigate microplastic ingestion in planktonic foragers, providing a characterization of spatio-temporal patterns of microplastic exposure in pelagic environments.

Analytical Characterization of the Intercalation of Neutral Molecules into Saponite.

Organo-modified layered materials characterization poses challenges due to their complexity and how other aspects such as contamination, preparation methods and degree of intercalation influence the properties of these materials. Consequently, a deep understanding of their interlayer organization is of utmost importance to optimize their applications. These materials can in fact improve the stability of photoactive molecules through intercalation, avoiding the quenching of their emission at the solid state, to facilitate their use in sensors or other devices. Two synthetic methods for the preparation of saponites with a cationic surfactant (CTABr) and a neutral chromophore (Fluorene) were tested and the obtained products were initially characterized with several complementary techniques (XRPD, SEM, TGA, IR, UV-Vis, Fluorescence and Raman spectroscopy), but a clear understanding of the organization of the guest molecules in the material could not be obtained by these techniques alone. This information was obtained only by thermogravimetry coupled with gas chromatography and mass spectroscopy (TGA-GC-MS) which allowed identifying the species present in the sample and the kind of interaction with the host by distinguishing between intercalated and adsorbed on the surface.

Following the fate of microplastic in four abiotic and biotic matrices along the Ticino River (North Italy).

Microplastics (MPs) are emerging contaminants in freshwater systems that have already attracted much scientific interest, but little attention has been paid to a multi-matrix analysis of MP occurrences along the length of a river. The present research provides the first record of MP contamination of four abiotic and biotic matrices from a river ecosystem simultaneously analysed. MPs were isolated and identified by micro-Fourier Transform Infrared (µ-FTIR) spectroscopy from samples collected along the Ticino River in North Italy during spring 2019. Abiotic samples were surface water (n = 18, 33 MPs m-3) and sediment (n = 18, 11 MPs kg-1), while biological samples consisted of stomach and gut content of fish (n = 18, wels catfish, Silurus glanis, 0.032 MPs g-1) and macroinvertebrates (n = 90, caddisfly larvae, Hydropsychidae, 0.03 MPs mg-1). MPs were found in biota from all stations; 44% of fish and 61% of macroinvertebrate samples contained MPs. The calculated unit-consistent concentration ratios indicate that both S. glanis and Hydropsychidae larvae had a consistent higher amount of MPs than their respective medium (sediment and water), strongly suggesting an efficient uptake pathway into organisms. MP levels in surface water, sediment, fish and macroinvertebrates were not correlated and did not increase with the river's length. From our mass balance calculations, the Ticino River transports a consistent amount of MP (yearly load of 3.40 × 1011 ± 1.1 × 1011 MPs) to the Po River. This MP load was almost half than an estimated MP load from wastewater treatment plants (WWTPs). On that basis and supported by the finding that MP concentration in sediment was mostly opposed to that in surface water but was on average 750-fold higher compared to the water matrix, we surmise that the complex hydrological network of the Ticino River retains a consistent amount of MPs which might build up over time.

Surgical Treatment of Sprengel's Deformity: A Systematic Review and Meta-Analysis.

(1) Background: Sprengel's deformity (SD) is a rare congenital anomaly caused by failure in the descent of the scapula. We aimed to systematically review the current literature reporting data from children undergoing surgery for SD, in order to explore the rate of success and complications of the different surgical techniques, possibly providing recommendations about the management of SD in children. (2) Methods: we electronically searched the literature from Ovid, MEDLINE and the Cochrane Library databases. Demographic data, surgical procedures, outcomes and complications were analyzed. We categorized surgical procedures into five groups. (3) Results: 41 articles met the inclusion criteria, showing a poor overall study quality; 674 patients (711 shoulders) were analyzed. Green's and Woodward's procedures, both aiming the scapular relocation in a more anatomical position, were the most commonly used techniques. We counted 168 adverse events (18 major complications). The best clinical and cosmetic results seem to be achieved when surgery is performed in children aged less than eight years. (4) Conclusions: this paper represents the first systematic review reporting qualitative and quantitative data about the surgical treatment of SD. Surgery for SD seems to be effective in increasing the shoulder's range of motion and improving the cosmetic appearance in almost all cases, with a low rate of major complications.

Quantification of molecular weight discrimination in grafting to reactions from ultrathin polymer films by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

In the present study, a reliable and robust method was developed to quantify the molecular weight discrimination that can occur in grafting to reactions via indirect MALDI-TOF quantification of the molecular weights of grafted chains by comparing the characteristics of the polymeric material before the grafting reaction with those of the unreacted material recovered after grafting. Two polystyrene samples with different molecular weights and narrow molecular weight distributions were employed to prepare model blends that were grafted to silicon wafers and an analytical method was developed and validated to assess and quantify the modification of the molecular weight distribution that takes place during the grafting to process. Particular attention was paid to the standardization of the sample treatment and to find the best data collection and calibration methodologies in order to have statistically significant data even in the presence of a very scarce amount of the sample. Furthermore, to evaluate the accuracy of the analytical procedure, the lack of suitable standard and certified materials required a further experiment to be carried out by comparing the new optimized MALDI-TOF method and direct measurements using TGA-GC-MS on a model blend containing deuterated and hydrogenated polystyrene samples with appropriate molecular weights and distributions. The optimized method was applied on samples obtained by a thermally induced grafting to reaction from ultrathin polymer films and, for the first time, to our knowledge, an enrichment effect occurring in the ultrathin grafted layer obtained from a melt was evidenced.

Cell instructive Liquid Crystalline Networks for myotube formation.

Development of biological tissues in vitro is not a trivial task and requires the correct maturation of the selected cell line. To this aim, many attempts were done mainly by mimicking the biological environment using micro/nanopatterned or stimulated scaffolds. However, the obtainment of functional tissues in vitro is still far from being achieved. In contrast with the standard methods, we here present an easy approach for the maturation of myotubes toward the reproduction of muscular tissue. By using liquid crystalline networks with different stiffness and molecular alignment, we demonstrate how the material itself can give favorable interactions with myoblasts helping a correct differentiation. Electrophysiological studies demonstrate that myotubes obtained on these polymers have more adult-like morphology and better functional features with respect to those cultured on standard supports. The study opens to a platform for the differentiation of other cell lines in a simple and scalable way.

The Rizzoli Multiple Osteochondromas Classification revised: describing the phenotype to improve clinical practice.

Multiple osteochondromas (MO) is a rare disorder, characterized by benign osteocartilaginous tumors (osteochondromas), arising from the perichondrium of bones. The osteochondromas increase during growth, frequently causing deformities and limitations. Our study aims to analyze the data captured by the Registry of Multiple Osteochondromas, to refine Istituto Ortopedico Rizzoli (IOR) Classification, providing a representative picture of the phenotypic manifestations throughout the lifespan. We conducted a single-institution cross-sectional study. Patients were categorized according to IOR Classification, which identifies three patients' classes on the presence/absence of deformities and/or limitations. The present dataset was compared with our previously published data, to refine the classification. Nine hundred sixty-eight patients were included: 243 children (<10 years), 136 adolescents (10-15 years), and 589 adults. Of the entire population, half patients presented at least one deformity, and one quarter reported at least one limitation. Compared with our previous study, the amount of children was more than doubled and the percentage of mild/moderate cases was notably increased, giving a better disease overview throughout the lifespan and suggesting a different cut-off for dividing Class II in subclasses. We confirmed that MO is characterized by phenotypic heterogeneity, suggesting that an early classification of the disease may offer a useful tool to follow disease pattern and evolution, to support clinical practice, and to propose timely interventions.

Outcomes of Temporary Hemiepiphyseal Stapling for Correcting Genu Valgum in Children with Multiple Osteochondromas: A Single Institution Study.

BACKGROUND: Multiple osteochondromas is a rare skeletal disorder characterized by the presence of osteocartilaginous protrusions causing bony deformities, especially around the knee. Guided growth by temporary hemiepiphyseal stapling is the treatment of choice to correct the deformity by modulating the residual physeal growth of the lower limbs. Although this procedure is increasingly practiced, inconclusive evidence exists regarding its effectiveness in children with multiple osteochondromas. The study aims to compare the outcomes of temporary hemiepiphyseal stapling for correcting genu valgum in children with multiple osteochondromas vs. idiopathic cases. METHODS: In this retrospective cohort study, we included patients admitted at a single institution from 2008 to 2018. A total of 97 children (77 idiopathic, 20 multiple osteochondromas) were enclosed, accounting for 184 limbs treated by temporary hemiepiphyseal stapling. We investigated if children with multiple osteochondromas had a similar successful rate of correction, rate of complications, and correction velocity compared to children with idiopathic genu valgum. RESULTS: Overall, 151 limbs (82%) achieved complete correction or overcorrection, with idiopathic cases having a significantly higher rate of success compared to pathologic cases (88% vs. 55%; p < 0.001). In addition, multiple osteochondromas children sustained a higher rate of major complications (p = 0.021) and showed significantly lower correction velocity (p = 0.029). CONCLUSION: Temporary hemiepiphyseal stapling is effective in both idiopathic and multiple osteochondromas children, although the latter often achieved incomplete correction, had a higher risk of complications, and required a longer time of stapling. We suggest to anticipate the timing of intervention; otherwise, children with multiple osteochondromas and severe valgus deformity, approaching skeletal maturity, could undergo combined femoral and tibial stapling.

Neglected Fractures of the Lateral Humeral Condyle in Children; Which Treatment for Which Condition?

BACKGROUND: Neglected fractures of the lateral humeral condyle (LHC) are misdiagnosed or insufficiently treated fractures, presenting later than 3 weeks after injury. The management of neglected LHC fractures in children remains controversial. METHODS: Twenty-seven children were included in this retrospective study. Charts and medical records were investigated for demographics, time interval between injury and treatment, and type of treatment. Baseline radiographs were assessed for fracture grading and displacement. Final radiographs were investigated for bone healing, avascular necrosis, elbow deformities and growth disturbances. Complications were classified by the Clavien-Dindo-Sink (CDS) system. Outcomes were assessed according to the Dhillon Score (DhiS) and Mayo Elbow Performance Score (MEPS). RESULTS: The mean time from injury to presentation was 27 months. Treatments included nonoperative management (6 patients), "in-situ" fixation (7 patients), open reduction and internal fixation (11 patients) and corrective osteotomy (3 patients). The mean follow-up was 7 years (range: 2-16). Overall, we observed complications in 16 patients (59%); six complications were considered major (22%) and occurred in Weiss Grade 3 fractures, with lateral displacement ≥5 mm. At the latest follow-up, pain and functional scores improved in 23 of 27 patients (85%). Mean MEPS increased from an average of 62 points preoperatively to 98 points postoperatively, while mean DhiS improved on average from 5 to 8 points. CDS score and time interval between injury and treatment were independent predictors of MEPS and DhiS. CONCLUSION: Our study describes outcomes from a cohort of children undergoing different treatments for neglected LHC fractures. Prolonged time interval between injury and treatment and perioperative major complications negatively impacted the treatment outcomes. Our findings strengthen the requirement for widely agreed guidelines of surgical management in neglected LHC fractures.

Microplastic Contamination in Snow from Western Italian Alps.

Recent studies have documented the presence of microplastics (MPs) in remote areas, including soils or sediments collected in mountain and glacier environments, but information on their presence in snow is scant. The present study aimed at exploring the presence of MPs in residual snow collected in four locations of the Aosta Valley (Western Italian Alps), with different accessibility and human presence. Overall, the µ-FTIR analyses confirmed the presence of 18 MPs in snow, 7 (39%) items were fibres, while 11 (61%) were fragments. Polyethylene (PE; 7 MPs) was the main polymer, followed by polyethylene terephthalate (PET; 3 MPs), high density PE (HDPE; 3 MPs), polyester (2 MPs), while only 1 MP made by low density PE, polypropylene and polyurethane were found. The mean (± SE) concentration of MPs in snow ranged between 0.39 ± 0.39 MPs/L and 4.91 ± 2.48 MPs/L, with a mean of 2.32 ± 0.96 MPs/L for the sampling locations. The concentration of MPs did not statistically differ among locations. Our results suggest that MPs presence in high-mountain ecosystems might depend on deposition through atmospheric precipitations or local sources due to human activities. For these reasons, policies aiming at reducing plastic use and dispersal in mountain areas may be effective in preventing local MP contamination.

Elastomeric Electrospun Scaffolds of a Biodegradable Aliphatic Copolyester Containing PEG-Like Sequences for Dynamic Culture of Human Endothelial Cells.

In the field of artificial prostheses for damaged vessel replacement, polymeric scaffolds showing the right combination of mechanical performance, biocompatibility, and biodegradability are still demanded. In the present work, poly(butylene-co-triethylene trans-1,4-cyclohexanedicarboxylate), a biodegradable random aliphatic copolyester, has been synthesized and electrospun in form of aligned and random fibers properly designed for vascular applications. The obtained materials were analyzed through tensile and dynamic-mechanical tests, the latter performed under conditions simulating the mechanical contraction of vascular tissue. Furthermore, the in vitro biological characterization, in terms of hemocompatibility and cytocompatibility in static and dynamic conditions, was also carried out. The mechanical properties of the investigated scaffolds fit within the range of physiological properties for medium- and small-caliber blood vessels, and the aligned scaffolds displayed a strain-stiffening behavior typical of the blood vessels. Furthermore, all the produced scaffolds showed constant storage and loss moduli in the investigated timeframe (24 h), demonstrating the stability of the scaffolds under the applied conditions of mechanical deformation. The biological characterization highlighted that the mats showed high hemocompatibility and low probability of thrombus formation; finally, the cytocompatibility tests demonstrated that cyclic stretch of electrospun fibers increased endothelial cell activity and proliferation, in particular on aligned scaffolds.

Occurrence of microplastics in pellets from the common kingfisher (Alcedo atthis) along the Ticino River, North Italy.

Previous research has reported avian plastic ingestion in marine bird species. Yet, while research attention on plastic pollution is shifting from marine to freshwater ecosystems, very few information on plastic ingestion is available for freshwater birds. Here, we examined the presence of microplastic in regurgitated pellets of the common kingfisher (Alcedo atthis) collected along the Ticino River (North Italy). In total, 133 kingfisher's pellets were examined between March and October 2019 from 54 transects along the river. Plastic elements were detected and identified by visual inspection followed by µ-FTIR and SEM-EDS. Overall, we found 12 (micro)plastics from at least three different polymers in 7.5% of the pellets. This study provides the first report of plastic uptake of this bird species. It highlights the importance of spectroscopic techniques in plastic monitoring studies in order to avoid misidentification of items found. Documenting the presence of plastic ingestion by top carnivores such as fish-eating birds is necessary to understand the pervasiveness and impact of (micro)plastic pollution in food webs of freshwater ecosystems.

The natural history of multiple osteochondromas in a large Italian cohort of pediatric patients.

IMPORTANCE: Multiple osteochondromas is a rare hereditary skeletal disorder, characterized by bony protrusions arising from growth plates on long bones during skeletal development. The disorder frequently leads to diminished stature, deformities and functional limitations. Understanding of the natural history of multiple osteochondromas and its evolution in children and adolescents is limited. OBJECTIVE: To provide valuable information on the natural history of multiple osteochondromas, to inform recommendations for treatment and prevent impairments caused by osteochondromas. DESIGN: This retrospective cohort study in children with multiple osteochondromas includes longitudinal data collected from first to last follow-up visit for patient demographics, and over 36 months for disease evolution. SETTING: Data were collected from the Registry of Multiple Osteochondromas, which includes data from circa 1200 patients with multiple osteochondromas treated from 2003 to 2017 at IRCCS Istituto Ortopedico Rizzoli in Bologna. PARTICIPANTS: Patients ≤18 years with multiple osteochondromas, who provided written informed consent and had data for ≥1 12-month follow-up visit. MAIN OUTCOME(S) AND MEASUREMENT(S): Demographics, clinical features, incidence of surgeries, and disease evolution (progression or regression) were assessed. Results were summarized using descriptive statistics, annual rates of new clinical features and surgeries, and Kaplan-Meier estimates. Patient height was evaluated following Italian growth charts. RESULTS: 158 patients were included in these analyses. Throughout follow-up, 80.4% of patients developed new osteochondromas, 57.6% developed new deformities, 23.4% developed new functional limitation(s). New osteochondroma(s) were developed by 28.5% patients by Month 12, 39.9% at Month 24, 50% at Month 36. Most new osteochondromas were detected in the younger population; patients aged 0-4 years underwent a significantly higher number of lesions within 12, 24 and 36 months of follow-up. The overall incidence of patients with ≥1 new deformity within 12 months was 17.7%, with incidences decreasing with increasing age (p = .023). In addition, the analyses on height highlight that 13 years is a cut off age for slow growth of the stature (p < .0005). At last follow-up visit, 46.2% of patients had disease progression, while regression (spontaneous and surgical) occurred in 7.6% (p = .007). CONCLUSIONS AND RELEVANCE: This natural history study reports the main set of clinically relevant data for patients with multiple osteochondromas during skeletal development, providing insight for patient management and development of therapeutic interventions.

Effect of shell structure of Ti-immobilized metal ion affinity chromatography core-shell magnetic particles for phosphopeptide enrichment.

Magnetic materials in sample preparation for shotgun phosphoproteomics offer several advantages over conventional systems, as the enrichment can be achieved directly in solution, but they still suffer from some drawbacks, due to limited stability and selectivity, which is supposed to be affected by the hydrophilicity of the polymeric supports used for cation immobilization. The paper describes the development of an improved magnetic material with increased stability, thanks to a two-step covering of the magnetic core, for the enrichment of phosphopeptides in biological samples. Four materials were prepared featuring a polymeric shell with tunable hydrophilicity, obtained by "grafting from" polymerization of glycidyl methacrylate with 0-8.3% of polyethylene glycol methacrylate (PEGMA), the latter used to modulate the hydrophilicity of the material surface. Finally, the materials were functionalized with iminodiacetic acid for Ti4+ ion immobilization. The materials were analyzed for their composition by a combination of CHN elemental analysis and thermogravimetric analysis, also hyphenated to gas chromatography and mass spectrometric detection. Surface characteristics were evaluated by water contact angle measurements, scanning electron microscopy and energy dispersive X-ray spectrometry. These materials were applied to the enrichment of phosphopeptides from yeast protein digests. Peptides were identified by proteomics techniques using nano-high performance liquid chromatography coupled to mass spectrometry and bioinformatics. Qualitatively the peptides identified by the four systems were comparable, with 1606-1693 phosphopeptide identifications and a selectivity of 47-54% for all materials. The physico-chemical features of the identified peptides were also the same for the four materials. In particular, the grand average of hydropathy index values indicated that the enriched phosphopeptides were hydrophilic (ca. 90%), and only some co-enriched non-phosphorylated peptides were hydrophobic (21-28%), regardless of the material used for enrichment. Peptides had a pI ≤ 7, which indicated a well-known bias for acidic peptides binding, attributed to the interaction with the metal center itself. The results indicated that the enrichment of phosphopeptides and the co-enrichment of non-phosphorylated peptides is mainly driven by interactions with Ti4+ and does not depend on the amount of PEGMA chains in the polymer shell.

Opposite Self-Folding Behavior of Polymeric Photoresponsive Actuators Enabled by a Molecular Approach.

The ability to obtain 3D polymeric objects by a 2D-to-3D shape-shifting method is very appealing for polymer integration with different materials, from metals in electronic devices to cells in biological studies. Such functional reshaping can be achieved through self-folding driven by a strain pattern designed into the molecular network. Among polymeric materials, liquid crystalline networks (LCNs) present an anisotropic molecular structure that can be exploited to tailor internal strain, resulting in a natural non-planar geometry when prepared in the form of flat films. In this article, we analyze the influence of different molecular parameters of the monomers on the spontaneous shape of the polymeric films and their deformation under different stimuli, such as heating or light irradiation. Modifying the alkilic chains of the crosslinkers is a simple and highly effective way to increase the temperature sensitivity of the final actuator, while modifying ester orientation on the aromatic core interestingly acts on the bending direction. Combining such effects, we have demonstrated that LCN stripes made of different monomeric mixtures originate complex non-symmetric deformation under light activation, thus opening up new applications in photonic and robotics.