Comparison of Synthetic Pathways for Obtaining Fluorescent Nanomaterials Based on Halloysite and Carbon Dots for Potential Biological Sensing.

Recently, fluorescent sensors have gained considerable attention due to their high sensitivity, low cost and noninvasiveness. Among the different materials that can be used for this purpose, carbon dots (CDs) represent valuable candidates for applications in sensing. These, indeed, are easily synthesized, show high quantum yield and are highly biocompatible. However, it was pointed out that the photoluminescence properties of these nanomaterials are strictly dependent on the synthetic and purification methods adopted. The presence of halloysite nanotubes (HNTs), a natural, low cost and biocompatible clay mineral, has been found to be efficient in obtaining small and highly monodispersed CDs without long and tedious purification techniques. Herein, we report the comparison of synthetic pathways for obtaining halloysite-N-doped CDs (HNTs-NCDs) that could be used in biological sensing. One was based on the synthesis of N-doped CDs by a bottom-up approach on HNTs' surface by a MW pyrolysis process; the other one was based on the post-modification of pristine N-doped CDs with halloysite derivatives. The evaluation of the best synthetic route was performed by different physico-chemical techniques. It was found that the bottom-up approach led to the formation of N-doped CDs with different functional groups onto the HNTs' surface. This evidence was also translated in the different fluorescence quantum yields and the existence of several functional groups in the obtained materials was investigated by potentiometric titrations. Furthermore, the ability of the synthesized nanomaterials as sensors for Fe3+ ions detection was assessed by spectroscopic measurements, and the cellular uptake was verified by confocal/fluorescence microscopies as well.

An Electroactive and Self-Assembling Bio-Ink, based on Protein-Stabilized Nanoclusters and Graphene, for the Manufacture of Fully Inkjet-Printed Paper-Based Analytical Devices.

Hundreds of new electrochemical sensors are reported in literature every year. However, only a few of them makes it to the market. Manufacturability, or rather the lack of it, is the parameter that dictates if new sensing technologies will remain forever in the laboratory in which they are conceived. Inkjet printing is a low-cost and versatile technique that can facilitate the transfer of nanomaterial-based sensors to the market. Herein, an electroactive and self-assembling inkjet-printable ink based on protein-nanomaterial composites and exfoliated graphene is reported. The consensus tetratricopeptide proteins (CTPRs), used to formulate this ink, are engineered to template and coordinate electroactive metallic nanoclusters (NCs), and to self-assemble upon drying, forming stable films. The authors demonstrate that, by incorporating graphene in the ink formulation, it is possible to dramatically improve the electrocatalytic properties of the ink, obtaining an efficient hybrid material for hydrogen peroxide (H2 O2 ) detection. Using this bio-ink, the authors manufactured disposable and environmentally sustainable electrochemical paper-based analytical devices (ePADs) to detect H2 O2 , outperforming commercial screen-printed platforms. Furthermore, it is demonstrated that oxidoreductase enzymes can be included in the formulation, to fully inkjet-print enzymatic amperometric biosensors ready to use.

A journey into the world of small RNAs in the arbuscular mycorrhizal symbiosis.

Arbuscular mycorrhizal (AM) symbiosis is a mutualistic interaction between fungi and most land plants that is underpinned by a bidirectional exchange of nutrients. AM development is a tightly regulated process that encompasses molecular communication for reciprocal recognition, fungal accommodation in root tissues and activation of symbiotic function. As such, a complex network of transcriptional regulation and molecular signaling underlies the cellular and metabolic reprogramming of host cells upon AM fungal colonization. In addition to transcription factors, small RNAs (sRNAs) are emerging as important regulators embedded in the gene network that orchestrates AM development. In addition to controlling cell-autonomous processes, plant sRNAs also function as mobile signals capable of moving to different organs and even to different plants or organisms that interact with plants. AM fungi also produce sRNAs; however, their function in the AM symbiosis remains largely unknown. Here, we discuss the contribution of host sRNAs in the development of AM symbiosis by considering their role in the transcriptional reprogramming of AM fungal colonized cells. We also describe the characteristics of AM fungal-derived sRNAs and emerging evidence for the bidirectional transfer of functional sRNAs between the two partners to mutually modulate gene expression and control the symbiosis.

Solubility-consistent force field simulations for aqueous metal carbonate systems using graphical processing units.

Crystallization of alkaline earth metal carbonates from water is important for biomineralization and environmental geochemistry. Here, large-scale computer simulations are a useful approach to complement experimental studies by providing atomistic insights and even by quantitatively determining the thermodynamics of individual steps. However, this is dependent on the existence of force field models that are sufficiently accurate while being computationally efficient enough to sample complex systems. Here, we introduce a revised force field for aqueous alkaline earth metal carbonates that reproduces both the solubilities of the crystalline anhydrous minerals, as well as the hydration free energies of the ions. The model is also designed to run efficiently on graphical processing units thereby reducing the cost of such simulations. The performance of the revised force field is compared against previous results for important properties relevant to crystallization, including ion-pairing and mineral-water interfacial structure and dynamics. This article is part of a discussion meeting issue 'Supercomputing simulations of advanced materials'.

The Covalent Functionalization of Surface-Supported Graphene: An Update.

In the last decade, the use of graphene supported on solid surfaces has broadened its scope and applications, and graphene has acquire a promising role as a major component of high-performance electronic devices. In this context, the chemical modification of graphene has become essential. In particular, covalent modification offers key benefits, including controllability, stability, and the facility to be integrated into manufacturing operations. In this Review, we critically comment on the latest advances in the covalent modification of supported graphene on substrates. We analyze the different chemical modifications with special attention to radical reactions. In this context, we review the latest achievements in reactivity control, tailoring electronic properties, and introducing active functionalities. Finally, we extended our analysis to other emerging 2D materials supported on surfaces, such as transition metal dichalcogenides, transition metal oxides, and elemental analogs of graphene.

Concluding remarks: Chemistry of 2-dimensional materials: beyond graphene.

Since graphene was exfoliated in 2004, two-dimensional (2D) materials have received great attention due to their physical and chemical properties associated with their nanosized thickness and the correlated quantum size effect. 2D planes allow the confinement of charge carriers, heat, and photons, leading to the remarkable electronic and optical properties of these materials. The Faraday Discussion"Chemistry of 2-dimensional materials: beyond graphene" has been an incredible showcase for a variety of highly interesting contributions in the field. This conference comprised a large number of aspects of the topic: from their synthesis and the study of their optical and physical properties to their numerous applications. These concluding remarks aim to capture the recent developments in 2D materials chemistry and physics that were presented and debated during this Faraday Discussion, and more generally in the research field in recent years. Particular attention will be paid to aspects like the synthesis of the materials, their toxicity and biodegradation, and some of their major applications in catalysis, as well as Li-ion batteries, water filtration and sensing. In addition we aim to highlight future challenges that still need to be addressed.

In silico analysis of fungal small RNA accumulation reveals putative plant mRNA targets in the symbiosis between an arbuscular mycorrhizal fungus and its host plant.

BACKGROUND: Small RNAs (sRNAs) are short non-coding RNA molecules (20-30 nt) that regulate gene expression at transcriptional or post-transcriptional levels in many eukaryotic organisms, through a mechanism known as RNA interference (RNAi). Recent studies have highlighted that they are also involved in cross-kingdom communication: sRNAs can move across the contact surfaces from "donor" to "receiver" organisms and, once in the host cells of the receiver, they can target specific mRNAs, leading to a modulation of host metabolic pathways and defense responses. Very little is known about RNAi mechanism and sRNAs occurrence in Arbuscular Mycorrhizal Fungi (AMF), an important component of the plant root microbiota that provide several benefits to host plants, such as improved mineral uptake and tolerance to biotic and abiotic stress. RESULTS: Taking advantage of the available genomic resources for the AMF Rhizophagus irregularis we described its putative RNAi machinery, which is characterized by a single Dicer-like (DCL) gene and an unusual expansion of Argonaute-like (AGO-like) and RNA-dependent RNA polymerase (RdRp) gene families. In silico investigations of previously published transcriptomic data and experimental assays carried out in this work provided evidence of gene expression for most of the identified sequences. Focusing on the symbiosis between R. irregularis and the model plant Medicago truncatula, we characterized the fungal sRNA population, highlighting the occurrence of an active sRNA-generating pathway and the presence of microRNA-like sequences. In silico analyses, supported by host plant degradome data, revealed that several fungal sRNAs have the potential to target M. truncatula transcripts, including some specific mRNA already shown to be modulated in roots upon AMF colonization. CONCLUSIONS: The identification of RNAi-related genes, together with the characterization of the sRNAs population, suggest that R. irregularis is equipped with a functional sRNA-generating pathway. Moreover, the in silico analysis predicted 237 plant transcripts as putative targets of specific fungal sRNAs suggesting that cross-kingdom post-transcriptional gene silencing may occur during AMF colonization.

Orthodontic-Orthopedic-Surgical Treatment of Syndromic Third Class: Proposal of a New Craniofacial Cephalometric Method.

The management of patients suffering from class III due to syndromic craniosynostosis requires a multidisciplinary team to prevent and correct the complex clinical features related to the syndrome. Among the main clinical features, the midface hypoplasia requires surgical advancement with a rigid external distraction device. The comparison of pre- and postdistraction lateral cephalometries is often difficult in these patients, because the craniofacial advancement mobilizes the landmarks routinely used in cephalometry. Aim of this study is to evaluate occlusal, maxillary, and facial changes obtained after the midface osteodistraction using as reference the PM plane, that does not undergo postsurgical spatial modifications.The before and after surgery lateral X-rays of 12 patients were compared to test the cephalometric protocol: 10 angles and 11 linear distances were evaluated.The cephalometric comparison before and after osteodistractions of syndromic class III, using as reference the Enlow's PM plane, has confirmed the data present in current literature, consisting in forward and downward movements of facial middle 3rd, with clockwise rotation of the splanchnocranium and increase of the facial heights. The use of the PM plane as reference could be the solution to problems that have been an obstacle for the study of occlusal and facial changes in patients affected by craniofacial dysostosis.

The virome of the arbuscular mycorrhizal fungus Gigaspora margarita reveals the first report of DNA fragments corresponding to replicating non-retroviral RNA viruses in fungi.

Arbuscular Mycorrhizal Fungi (AMF) are key components of the plant microbiota. AMF genetic complexity is increased by the presence of endobacteria, which live inside many species. A further component of such complexity is the virome associated to AMF, whose knowledge is still very limited. Here, by exploiting transcriptomic data we describe the virome of Gigaspora margarita. A BLAST search for viral RNA-dependent RNA polymerases sequences allowed the identification of four mitoviruses, one Ourmia-like narnavirus, one Giardia-like virus, and two sequences related to Fusarium graminearum mycoviruses. Northern blot and RT-PCR confirmed the authenticity of all the sequences with the exception of the F. graminearum-related ones. All the mitoviruses are replicative and functional since both positive strand and negative strand RNA are present. The abundance of the viral RNA molecules is not regulated by the presence or absence of Candidatus Glomeribacter gigasporarum, the endobacterium hosted by G. margarita, with the exception of the Ourmia-like sequence which is absent in bacteria-cured spores. In addition, we report, for the first time, DNA fragments corresponding to mitovirus sequences associated to the presence of viral RNA. These sequences are not integrated in the mitochondrial DNA and preliminary evidence seems to exclude integration in the nuclear genome.

Transmission of Penicillium aurantiogriseum partiti-like virus 1 to a new fungal host (Cryphonectria parasitica) confers higher resistance to salinity and reveals adaptive genomic changes.

We attempted to transfect six recently characterized virus species to protoplasts of Penicillium janczewskii and Chryphonectria parasitica. None of the recovered P. janczewskii colonies was positive for the transfected viruses, but Penicillium aurantiogriseum partiti-like virus 1 (PaPLV1) was detected in three distinct regenerated C. parasitica colonies. We screened the phenotype of the infected strains in up to 45 different conditions combining different media, salinity and temperatures: our results show that the infected strains grow slower than the virus- free in most of the tested conditions with the exception of halophilic stress in a specific nutrient combination media. We proceeded to characterize molecularly the population of distinct isolates of PaPLV1 infected C. parasitica through RNAseq: comparison to the viral population present in the original host - P. auratiogriseum - showed that two isolates accumulated non-synonymous mutations suggesting adaptation to the new host. RNAseq analyses identified a second genomic RNA segment and northern blot of RNA extracted from purified virus suspensions allowed establishing that PaPLV1 is at least bipartite in nature and that it forms isometric virions of circa 36-38 nm in diameter. In light of these new acquisitions, we discuss the taxonomic placement of PaPLV1 inside the Partitiviridae.

Fluidic Manufacture of Star-Shaped Gold Nanoparticles.

Star-shaped gold nanoparticles (StarAuNPs) are extremely attractive nanomaterials, characterized by localized surface plasmon resonance which could be potentially employed in a large number of applications. However, the lack of a reliable and reproducible synthetic protocols for the production of StarAuNPs is the major limitation to their spreading. For the first time, here we present a robust protocol to manufacture reproducible StarAuNPs by exploiting a fluidic approach. Star-shaped AuNPs have been synthesized by means of a seed-less protocol, employing ascorbic acid as reducing agent at room temperature. Moreover, the versatility of the bench-top microfluidic protocol has been exploited to afford hydrophilic, hydrophobic and solid-supported engineered StarAuNPs, by avoiding intermediate NP purifications.

Glyco-gold nanoparticles: synthesis and applications.

Glyco-gold nanoparticles combine in a single entity the peculiar properties of gold nanoparticles with the biological activity of carbohydrates. The result is an exciting nanosystem, able to mimic the natural multivalent presentation of saccharide moieties and to exploit the peculiar optical properties of the metallic core. In this review, we present recent advances on glyco-gold nanoparticle applications in different biological fields, highlighting the key parameters which inspire the glyco nanoparticle design.

Synthesis of Water Dispersible and Catalytically Active Gold-Decorated Cobalt Ferrite Nanoparticles.

Hetero-nanoparticles represent an important family of composite nanomaterials that in the past years are attracting ever-growing interest. Here, we report a new strategy for the synthesis of water dispersible cobalt ferrite nanoparticles (CoxFe3-xO4 NPs) decorated with ultrasmall (2-3 nm) gold nanoparticles (Au NPs). The synthetic procedure is based on the use of 2,3-meso-dimercaptosuccinic acid (DMSA), which plays a double role. First, it transfers cobalt ferrite NPs from the organic phase to aqueous media. Second, the DMSA reductive power promotes the in situ nucleation of gold NPs in proximity of the magnetic NP surface. Following this procedure, we achieved a water dispersible nanosystem (CoxFe3-xO4-DMSA-Au NPs) which combines the cobalt ferrite magnetic properties with the catalytic features of ultrasmall Au NPs. We showed that CoxFe3-xO4-DMSA-Au NPs act as an efficient nanocatalyst to reduce 4-nitrophenol to 4-aminophenol and that they can be magnetically recovered and recycled. It is noteworthy that such nanosystem is more catalytically active than Au NPs with equal size. Finally, a complete structural and chemical characterization of the hetero-NPs is provided.

Two-Dimensional and Three-Dimensional Cephalometry Using Cone Beam Computed Tomography Scans.

Lateral cephalometric radiograph produces a two-dimensional image with several drawbacks. Cone beam computed tomography (CBCT) allows obtaining a three-dimensional representation of the craniofacial structures and seems to overcome the problems of superimposition and magnification, providing more precision than two-dimensional methods. The aim of the current study was to test the intraobserver and interobserver reliability of linear and angular measurements performed on two-dimensional conventional cephalometric images and CBCT-generated cephalograms, and to evaluate if there is a statistically significant difference between the 2 methods of measurements. The sample group consisted of 24 adolescents with a pretreatment digital lateral radiograph and a corresponding CBCT image. A total of 16 cephalometric landmarks were identified and 17 widely used measurements (9 angular and 8 linear) were recorded by 2 independent observers. Intraobserver and interobserver reliability were assessed by calculating Pearson correlation coefficient. Student t-test was used to compare the 2 methods. The threshold for significance was set at P ≤ 0.05.Concerning the intraobserver and interobserver reliability, data showed a statistically significant correlation between all two-dimensional and three-dimensional measurements. The linear and angular measurements of two-dimensional and three-dimensional cephalometry were not statistically different. The results of the current study showed the reliability of both conventional two-dimensional and three-dimensional cephalometry. Linear and angular measurements from CBCT were found also to be similar to conventional measurements. Considering that conventional images deliver the lowest radiation doses to patients, the use of CBCT for orthodontic purposes should be limited.

The use of piezosurgery in cranial surgery in children.

Piezosurgery is an alternative surgical technique, now widely tested, that uses ultrasounds for bone cutting. This device uses ultrasounds to section hard tissues without harming surrounding soft tissues. The authors analyzed their experience in craniomaxillofacial procedures with piezosurgery. A comparison between operation timing and complication rates between piezosurgery and traditional cutting instruments has been performed. A total of 27 patients were examined (15 females and 12 males; average age, of 5.5 months) affected by craniosynostosis. The aim of this study was to analyze the advantages and disadvantages of piezosurgery in pediatric craniofacial procedures. Piezoelectric device in this study has shown being a valid instrument for bone cutting in accurate procedures, because it allows performing a more precise and safer cutting, without the risk of harming surrounding tissues.

A simple method to inset and position polyurethane-covered breast implants.

BACKGROUND: Polyurethane-covered breast implants have been used increasingly for cosmetic and revision breast surgery. The incision for insertion should be of minimal length and the placement of these implants in the pocket can be more difficult than that of conventional implants because of the highly adherent textured surface of the polyurethane external layer that grasps the surrounding tissues. The use of a sterile plastic insertion sleeve that is open on both sides is suggested by the manufacturer to overcome the friction between the polyurethane implant and the skin and surrounding tissues. METHODS: A new method to facilitate polyurethane implant insertion and adjustment in all cases of primary breast augmentation and revision surgery is presented. After the implant, which is in the sleeve, is located in the pocket, the plastic sleeve is filled with saline and antibiotics so the solution lubricates the surface around the implant. The sleeve is then twisted so that the solution is squeezed inside the pocket while the sleeve itself is pulled back and removed. RESULTS: Between 2010 and 2013, this method was used in 73 cases of primary augmentation and revision breast surgery without any complications. CONCLUSION: The method described here allows for easier removal of the plastic sleeve during polyurethane implant insertion without any complications or evidence of implant migration or rotation at follow-up. LEVEL OF EVIDENCE IV: This journal requires that authors assign a level of evidence to each submission to which Evidence-Based Medicine rankings are applicable. This excludes Review Articles, Book Reviews, and manuscripts that concern Basic Science, Animal Studies, Cadaver Studies, and Experimental Studies. For a full description of these Evidence-Based Medicine ratings, please refer to the Table of Contents or the online Instructions to Authors http://www.springer.com/00266 .

Augmentation mammoplasty/mastopexy: lessons learned from 107 aesthetic cases.

BACKGROUND: One-stage augmentation/mastopexy entails the challenge of augmenting breast volume with an implant while resecting excess skin. Although both augmenting and lifting the breast in a one-stage operation is gaining in popularity, its safety and its efficacy are still under debate and merit deeper evaluation. METHODS: We retrospectively reviewed our experience over a 5-years period with patients who underwent augmentation mammoplasty/mastopexy with the specific objectives of documenting their outcomes and formulating algorithms for safe, simple, and effective operative strategies to manage such patients. Our surgical approach to augmentation/mastopexy breast ptosis was described step by step. Patient satisfaction with the results was also evaluated. RESULTS: One hundred seven patients underwent successful simultaneous augmentation/mastopexy surgery. Sixty-nine underwent primary breast surgery and 38 underwent secondary breast surgery. In 12 cases a periareolar mastopexy scar was used, while in 51 patients a vertical approach was preferred; in 11 and 33 patients a short "T" and an inverted "T" scar mastopexy was necessary, respectively. Few complications were observed, with a very low overall complication rate (14 %) and a reoperation rate of 12.1 % at 14.7 months. Patient satisfaction with the results of this procedure was extremely high. CONCLUSIONS: Simultaneous augmentation/mastopexy is an effective and versatile way to lift the NAC, tighten the breast skin, increase breast projection, and fill in the upper pole. Our technique of simultaneous breast mastopexy after augmentation through a lower periareolar approach showed excellent correction of pre-existing ptosis, making this method highly reliable because the intraoperative tailor-tacking was customized to the patient, implant size, and projection.