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The lack of solubility in water and the formation of aggregates hamper many opportunities for technological exploitation of C 60 . Here, different peptides were designed and synthesized with the aim of monomolecular dispersion of C 60 in water. Phenylalanines were used as recognizing moieties, able to interact with C 60 through π-π stacking, while a varying number of glycines were used as spacers, to connect the two terminal phenylalanines. The best performance in the dispersion of C 60 was obtained with the FGGGF peptidic nanotweezer at a pH of 12. A full characterization of this adduct was carried out. The peptides disperse C 60 in water with high efficiency, and the solutions are stable for months both in pure water and in physiological environments. NMR measurements demonstrated the ability of the peptides to interact with C 60 . AFM measurements showed that C 60 is monodispersed. Electrospray ionization mass spectrometry determined a stoichiometry of C 60 @(FGGGF) 4 . Molecular dynamics simulations showed that the peptides assemble around the C 60 cage, like a candy in its paper wrapper, creating a supramolecular host able to accept C 60 in the cavity. The peptide-wrapped C 60 is fully biocompatible and the C 60 "dark toxicity" is eliminated. C 60 @(FGGGF) 4 shows visible light-induced reactive oxygen species (ROS) generation at physiological saline concentrations and reduction of the HeLa cell viability in response to visible light irradiation.

Ancillary factors, not directly related to treatment, often play a significant role by affecting therapeutic outcome. A search of the literature was conducted including words related to the placebo phenomenon and orofacial diseases. Therefore, critical factors have been grouped into three major categories: (a) the natural course of the diseases; (b) the regression of the symptoms to their mean intensity; and (c) placebo response. This topical narrative review describes the elements mentioned above, provides an up-to-date overview of the hot topics and gaps in the field and indicates developing and future research direction of the orofacial pain field. Such a knowledge might be positively used during daily clinical practice to optimise the management of orofacial pain diseases, as well as in conducting future clinical trials for validating new interventions., (© 2018 John Wiley & Sons Ltd.)

Headache attributed to temporomandibular disorders (TMDH) is defined as a secondary headache by the International Classification of Headache Disorders 3rd edition (ICHD-3)., Objective: The objective of this case-control study is to investigate the phenotypic characteristics of chronic TMD with and without TMDH. We hypothesize that chronic TMD with TMDH is associated with increased number of bodily pain conditions, more painful sites in the head and neck region, and greater TMD pain intensity., Methods: This is a retrospective cross-sectional review of the medical records of consecutive patients who sought treatment at the University of North Carolina Orofacial Pain Clinic between 2013 and 2014. The inclusion criterion was a diagnosis of myalgia or arthralgia according to the Research Diagnostic Criteria for Temporomandibular Disorders. In addition, cases had a diagnosis of TMDH according to the ICHD-3 criteria. Data on the presence and the number of self-reported bodily pain conditions (such as fibromyalgia and low back pain), pain intensity, number of painful sites in the head and neck upon palpation, and TMD pain onset were analyzed., Results: A total of 295 records were reviewed. Thirty-four (29.3%) patients fulfilled inclusion criteria for cases (TMD+TMDH) and 82 (70.7%) for controls (TMD-TMDH). Cases reported greater number of bodily pain conditions than controls, with a mean of 1.97 ± 1.50 and 1.26 ± 1.28 of bodily pain conditions, respectively (P = .012, OR = 1.43 [95% CI 1.07-1.92]). In fact, 55.9% of cases reported at least 2 comorbid pain conditions compared to 37.8% controls (P = .044). Compared to controls (8.65 ± 5.32), cases (13.05 ± 4.46) exhibited greater number of painful sites upon palpation in the head and neck region (P < .0001, OR = 1.18 [95% CI 1.09-1.30]), and greater TMD pain intensity, with a mean of 6.00 ± 2.17 for cases and 5.09 ± 2.14 for controls (P = .041, OR = 1.22 [95% CI 1.01-1.47])., Conclusion: In a population of patients with chronic TMD seeking pain management, TMDH was significantly associated with an increased number of self-reported bodily pain conditions, a greater number of painful sites in the head and neck regions, and higher TMD pain intensity., (© 2018 American Headache Society.)

Hybrid systems have great potential for a wide range of applications in chemistry, physics and materials science. Conjugation of a biosystem to a molecular material can tune the properties of the components or give rise to new properties. As a workhorse, here we take a C60@lysozyme hybrid. We show that lysozyme recognizes and disperses fullerene in water. AFM, cryo-TEM and high resolution X-ray powder diffraction show that the C60 dispersion is monomolecular. The adduct is biocompatible, stable in physiological and technologically-relevant environments, and easy to store. Hybridization with lysozyme preserves the electrochemical properties of C60. EPR spin-trapping experiments show that the C60@lysozyme hybrid produces ROS following both type I and type II mechanisms. Due to the shielding effect of proteins, the adduct generates significant amounts of 1O2 also in aqueous solution. In the case of type I mechanism, the protein residues provide electrons and the hybrid does not require addition of external electron donors. The preparation process and the properties of C60@lysozyme are general and can be expected to be similar to other C60@protein systems. It is envisaged that the properties of the C60@protein hybrids will pave the way for a host of applications in nanomedicine, nanotechnology, and photocatalysis.

The high hydrophobicity of fullerenes and the resulting formation of aggregates in aqueous solutions hamper the possibility of their exploitation in many technological applications. Noncovalent bioconjugation of fullerenes with proteins is an emerging approach for their dispersion in aqueous media. Contrary to covalent functionalization, bioconjugation preserves the physicochemical properties of the carbon nanostructure. The unique photophysical and photochemical properties of fullerenes are then fully accessible for applications in nanomedicine, sensoristic, biocatalysis and materials science fields. However, proteins are not universal carriers. Their stability depends on the biological conditions for which they have evolved. Here we present two model systems based on pepsin and trypsin. These proteins have opposite net charge at physiological pH. They recognize and disperse C 60 in water. UV-Vis spectroscopy, zeta-potential and atomic force microscopy analysis demonstrates that the hybrids are well dispersed and stable in a wide range of pH&rsquo;s and ionic strengths. A previously validated modelling approach identifies the protein-binding pocket involved in the interaction with C 60 . Computational predictions, combined with experimental investigations, provide powerful tools to design tailor-made C 60 @proteins bioconjugates for specific applications.

Fe-EDDHSA/CaCO 3 hybrid crystals are synthesized and tested in vitro to determine their effect in treating iron chlorosis in kiwifruit plants, used as a proof of concept. Under the alkaline conditions provided by the calcareous substrate, plants release protons that dissolve the hybrids and trigger Fe uptake. These CaCO 3 hybrids represent a new system for active molecule delivery in agriculture.

C 60 @lysozyme showed significant visible light-induced singlet oxygen generation in water, indicating the potential of this hybrid as an agent for photodynamic therapy. The reactive oxygen species (ROS) concentration generated by C 60 @lysozyme during irradiation depends on the light source, the irradiation time and the concentration of the hybrid. C 60 @lysozyme significantly reduced the HeLa cell viability in response to visible light irradiation. The generation of H 2 O 2 , due to the photoactivity of C 60 @lysozyme, causes cell death via easy permeation of hydrogen peroxide through the cell membrane and activation of endogenous ROS production.

We present herein the preparation of four different hydrogels based on the pseudopeptide gelator Fmoc-l-Phe-d-Oxd-OH (Fmoc=fluorenylmethyloxycarbonyl), either by changing the gelator concentration or adding graphene oxide (GO) to the water solution. The hydrogels have been analysed by rheological studies that demonstrated that pure hydrogels are slightly stronger compared to GO-loaded hydrogels. Then the hydrogels efficiency to trap the cationic methylene blue (MB) and anionic eosin Y (EY) dyes has been analyzed. MB is efficiently trapped by both the pure hydrogel and the GO-loaded hydrogel through π-π interactions and electrostatic interactions. In contrast, the removal of the anionic EY is achieved in less satisfactory yields, due to the unfavourable electrostatic interactions between the dye, the gelator and GO., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Objectives: To perform a review of the literature of published articles assessing the role of genetic factors in the etiology of temporomandibular disorders (TMDs)., Methods: A PubMed search was carried out by looking for all controlled clinical trials related to the topic and limiting the search to English language and humans. The references from the studies included and those from review articles were also examined for further relevant papers., Results: A total of 1999 articles were first identified, 24 of which were considered relevant to the topic. Two other papers were found while searching the references. While TMD signs and symptoms' co-occurrence was not found in subjects within the same family, many gene polymorphisms were shown to be associated with a higher or lower risk of TMD. Such genes were mainly related to serotonin activity and metabolism, Tcellreceptor pathway, catecholamine activity and metabolism, estrogen activity, folate metabolism, glutathione activity, ANKH gene, major histocompatibility complex, extracellular matrix metabolism, genes studied in the orofacial pain prospective evaluation risk and assessment (OPPERA) study, and related to cytokines activity and metabolism., Discussion: This new understanding of the pathophysiology of TMD can lead to a different treatment approach by identifying the subjects at higher risk for this pathology, and possibly by creating new drugs targeted at interfering with the expression of the genes that enhance such risk.

Ocean acidification is predicted to impact ecosystems reliant on calcifying organisms, potentially reducing the socioeconomic benefits these habitats provide. Here we investigate the acclimation potential of stony corals living along a pH gradient caused by a Mediterranean CO2 vent that serves as a natural long-term experimental setting. We show that in response to reduced skeletal mineralization at lower pH, corals increase their skeletal macroporosity (features >10 μm) in order to maintain constant linear extension rate, an important criterion for reproductive output. At the nanoscale, the coral skeleton's structural features are not altered. However, higher skeletal porosity, and reduced bulk density and stiffness may contribute to reduce population density and increase damage susceptibility under low pH conditions. Based on these observations, the almost universally employed measure of coral biomineralization, the rate of linear extension, might not be a reliable metric for assessing coral health and resilience in a warming and acidifying ocean.

Scleractinian corals are a major source of biogenic calcium carbonate, yet the relationship between their skeletal microstructure and mechanical properties has been scarcely studied. In this work, the skeletons of two coral species:solitary Balanophyllia europaea and colonial Stylophora pistillata, were investigated by nanoindentation. The hardness HIT and Young's modulus E(IT) were determined from the analysis of several load-depth data on two perpendicular sections of the skeletons: longitudinal (parallel to the main growth axis) and transverse. Within the experimental and statistical uncertainty,the average values of the mechanical parameters are independent on the section's orientation. The hydration state of the skeletons did not affect the mechanical properties. The measured values, EIT in the 76-77 GPa range, and H(IT) in the 4.9–5.1 GPa range, are close to the ones expected for polycrystalline pure aragonite. Notably, a small difference in H(IT) is observed between the species. Different from corals, single-crystal aragonite and the nacreous layer of the seashell Atrina rigida exhibit clearly orientation-dependent mechanical properties. The homogeneous and isotropic mechanical behaviour of the coral skeletons at the microscale is correlated with the microstructure,observed by electron microscopy and atomic force microscopy, and with the X-ray diffraction patterns of the longitudinal and transverse sections.

A general framework is provided that makes possible the estimation of time-dependent properties of a stochastic system moving far from equilibrium. The process is investigated and discussed in general terms of nonequilibrium thermodynamics. The approach is simple and can be exploited to gain insight into the dynamics of any molecular-level machine. As a case study, the dynamics of an artificial molecular rotary motor, similar to the inversion of a helix, which drives the motor from a metastable state to equilibrium, are examined. The energy path that the motor walks was obtained from the results of atomistic calculations. The motor undergoes unidirectional rotation and its entropy, internal energy, free energy, and net exerted force are given as a function of time, starting from the solution of Smoluchowski's equation. The rather low value of the organization index, that is, the ratio of the work done by the particle against friction during the unidirectional motion per available free energy, reveals that the motion is mainly subject to randomness, and the amount of energy converted to heat due to the directional motion is very small., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Four different force fields are examined for dynamic characteristics using cholesterol as a case study. The extent to which various types of internal degrees of freedom become thermodynamically relevant is evaluated by means of principal component analysis. More complex degrees of freedom (angle bending, dihedral rotations) show a trend towards force field independence. Moreover, charge assignments for membrane-embedded compounds are revealed to be critical with significant impact on biological reasoning.

A case of a patient with a fracture of the temporomandibular joint (TMJ) disk is reported. The patient presented with posterior bilateral open-bite and difficulty to chew due to lack of contact between the posterior teeth. Diagnosis of disk fracture of the right TMJ was made based on magnetic resonance imaging (MRI), with posterior displacement of the posterior fragment of the disk, causing the posterior open-bite, and anterior displacement of the anterior fragment of the disk. TMJ manipulation failed to reposition the posterior fragment of the disk, and the patient refused to undergo TMJ arthroscopy to try to remove it. After four months, the posterior open-bite was reduced, probably because of remodeling of the posterior TMJ capsule and extrusion of the molars and premolars. Contact with the patient was lost after that time.