Botulinum Toxin-A Infiltration to Control Post-Operative Pain after Mastectomy and Expander Reconstruction as Potentially Useful Tool: A Narrative Review.

Botulinum toxin-A (BTX-A), a neurotoxin produced by Clostridium botulinum, was assessed for relieving implant-related pectoralis major muscle's painful spasms. In detail, 100 units of BTX-A can reduce muscle activity and, as a consequence, muscle spasms. The latter is considered the leading cause of post-operative pain after the sub-pectoral tissue expansion, sometimes leading to early expanders' removal. In addition, women choosing post-mastectomy reconstruction surgery seem to suffer worse post-operative pain than those who stop at the mastectomy stage. However, there is no unanimous consensus concerning the potential benefits of BTX-A in reducing pain related to the sub-pectoral placement of tissue expanders in breast reconstruction due to the exiguity of evidence. Therefore, this review aims to describe BTX-A-related evidence in this reconstruction setting. NO LEVEL ASSIGNED: 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 www.springer.com/00266 .

Nanoactuator for Neuronal Optoporation.

Light-driven modulation of neuronal activity at high spatial-temporal resolution is becoming of high interest in neuroscience. In addition to optogenetics, nongenetic membrane-targeted nanomachines that alter the electrical state of the neuronal membranes are in demand. Here, we engineered and characterized a photoswitchable conjugated compound (BV-1) that spontaneously partitions into the neuronal membrane and undergoes a charge transfer upon light stimulation. The activity of primary neurons is not affected in the dark, whereas millisecond light pulses of cyan light induce a progressive decrease in membrane resistance and an increase in inward current matched to a progressive depolarization and action potential firing. We found that illumination of BV-1 induces oxidation of membrane phospholipids, which is necessary for the electrophysiological effects and is associated with decreased membrane tension and increased membrane fluidity. Time-resolved atomic force microscopy and molecular dynamics simulations performed on planar lipid bilayers revealed that the underlying mechanism is a light-driven formation of pore-like structures across the plasma membrane. Such a phenomenon decreases membrane resistance and increases permeability to monovalent cations, namely, Na+, mimicking the effects of antifungal polyenes. The same effect on membrane resistance was also observed in nonexcitable cells. When sustained light stimulations are applied, neuronal swelling and death occur. The light-controlled pore-forming properties of BV-1 allow performing "on-demand" light-induced membrane poration to rapidly shift from cell-attached to perforated whole-cell patch-clamp configuration. Administration of BV-1 to ex vivo retinal explants or in vivo primary visual cortex elicited neuronal firing in response to short trains of light stimuli, followed by activity silencing upon prolonged light stimulations. BV-1 represents a versatile molecular nanomachine whose properties can be exploited to induce either photostimulation or space-specific cell death, depending on the pattern and duration of light stimulation.

Extremely rare case of unilateral gigantomastia after hormonal stimulation treated with a modified wise pattern technique: A case report.

INTRODUCTION: Gigantomastia, characterized by excessive breast size (usually heavier than 2.5 kg), can result from various causes and significantly affect patients' lives. Surgical intervention is often required, and over time, several techniques have been developed for its treatment. These techniques aim to address the functional and aesthetic concerns associated with gigantomastia, providing relief to patients and improving their quality of life. PRESENTATION OF THE CASE: A 40-year-old primiparous housewife developed unilateral gigantomastia as a consequence of hormone therapy. To address this, a modified reduction mammoplasty procedure was undertaken, incorporating NAC (Nipple-Areola Complex) grafting. The reduction involved removing 3450 g of tissue, resulting in restored breast symmetry and enabling the patient to reintegrate into normal daily life. DISCUSSION: Compared to the traditional technique, the introduction of some modifications in the design allowed for the absence of complications such as dehiscence of the scar at the intersection of the T, the failure of the nipple graft attachment, and the maintenance of a conical shape over time, enabling complete symmetrization of the two breasts. CONCLUSION: The use of a modified version of the Thorek technique allowed for optimal functional and aesthetic restoration even in the case of a significantly disproportionate breast compared to the contralateral one, with no complications.

A membrane intercalating metal-free conjugated organic photosensitizer for bacterial photodynamic inactivation.

Photodynamic inhibition (PDI) of bacteria represents a powerful strategy for dealing with multidrug-resistant pathogens and infections, as it exhibits minimal development of antibiotic resistance. The PDI action stems from the generation of a triplet state in the photosensitizer (PS), which subsequently transfers energy or electrons to molecular oxygen, resulting in the formation of reactive oxygen species (ROS). These ROS are then able to damage cells, eventually causing bacterial eradication. Enhancing the efficacy of PDI includes the introduction of heavy atoms to augment triplet generation in the PS, as well as membrane intercalation to circumvent the problem of the short lifetime of ROS. However, the former approach can pose safety and environmental concerns, while achieving stable membrane partitioning remains challenging due to the complex outer envelope of bacteria. Here, we introduce a novel PS, consisting of a metal-free donor-acceptor thiophene-based conjugate molecule (BV-1). It presents several advantageous features for achieving effective PDI, namely: (i) it exhibits strong light absorption due to the conjugated donor-acceptor moieties; (ii) it exhibits spontaneous and stable membrane partitioning thanks to its amphiphilicity, accompanied by a strong fluorescence turn-on; (iii) it undergoes metal-free intersystem crossing, which occurs preferentially when the molecule resides in the membrane. All these properties, which we rationalized via optical spectroscopies and calculations, enable the effective eradication of Escherichia coli, with an inhibition concentration that is below that of current state-of-the-art treatments. Our approach holds significant potential for the development of new PS for controlling bacterial infections, particularly those caused by Gram-negative bacteria.

Activation of Solid-State Emission and Photostability through Molecular Confinement: The Case of Triptycene-Fused Quinacridone Dyes.

We report the facile, metal-free convergent synthesis and the characterization of novel quinacridone dyes in which two triptycene units end-cap and sterically confine the quinacridone chromophore. A precise comparison of the confined dyes with their known homologues reveals that the reduction of π-π interactions in triptycene-fused quinacridone dyes compared to classical quinacridone results not only in an increase of solubility and processability but also in an enhancement of fluorescence quantum yield and photostability in the solid state.

Green solvents, materials, and lead-free semiconductors for sustainable fabrication of perovskite solar cells.

Perovskite materials research has received unprecedented recognition due to its applications in photovoltaics, LEDs, and other large area low-cost electronics. The exceptional improvement in the photovoltaic conversion efficiency of Perovskite solar cells (PSCs) achieved over the last decade has prompted efforts to develop and optimize device fabrication technologies for the industrial and commercial space. However, unstable operation in outdoor environments and toxicity of the employed materials and solvents have hindered this proposition. While their optoelectronic properties are extensively studied, the environmental impacts of the materials and manufacturing methods require further attention. This review summarizes and discusses green and environment-friendly methods for fabricating PSCs, particularly non-toxic solvents, and lead-free alternatives. Greener solvent choices are surveyed for all the solar cell films, (i.e. electron and hole transport, semiconductor, and electrode layers) and their impact on thin film quality, morphology and device performance is explored. We also discuss lead content in perovskites, its environmental impact and sequestration routes, and progress in replacing lead with greener alternatives. This review provides an analysis of sustainable green routes in perovskite solar cell fabrication, discussing the impact of each layer in the device stack, via life cycle analysis.

Multigram-Scale Synthesis of Luminescent Cesium Lead Halide Perovskite Nanobricks for Plastic Scintillators.

Cesium lead halide perovskite nanocrystals of general formula CsPbX3 are having tremendous impact on a vast array of technologies requiring strong and tunable luminescence across the visible range and solutions processing. The development of plastic scintillators is just one of the many relevant applications. The syntheses are relatively simple but generally unsuitable to produce a large amount of material of reproducible quality required when moving from proof-of-concept scale to industrial applications. Wastes, particularly large amounts of lead-contaminated toxic and flammable organic solvents, are also an open issue. We describe a simple and reproducible procedure enabling the synthesis of luminescent CsPbX3 nanobricks of constant quality on a scale going from 0.12 to 8 g in a single batch. We also show complete recycling of the reaction wastes, leading to dramatically improved efficiency and sustainability.

Partition of the Reactive Species of the Suzuki-Miyaura Reaction between Aqueous and Micellar Environments.

The Suzuki-Miyaura reaction between the aryl halide (1) and the phenyl boronic acid (2), in the presence of the palladium(0) complex (3) as catalyst, gives the cross-coupling product (4) in quantitative yield when performed in basic aqueous solution of the nonionic surfactant Kolliphor-EL (K-EL). The partition between the aqueous and micellar environments of the species of this reaction has been investigated by means of Molecular Dynamics (MD) simulations. Starting from the K-EL molecules dispersed in water, a micelle model has been generated by MD simulations, adopting the 2016H66 force field. Reagent and product species have been described with the same force field, once the reliability of this force field has been tested comparing the n-octanol/water partition free energies calculated from the MD and Free Energy Perturbation (FEP) method with those obtained from the quantum-mechanical SMD method. The potential of mean force for the transfer process between water and the micellar phase of the different species has been calculated by the MD simulations and the Umbrella Sampling (US) method. The overall picture that emerges from these results confirms that the molecular species involved in this reaction prefers the micellar environment and concentrates in different but close zones of the micelle. This supports the experimental evidence that the use of suitable surfactant agents promotes reactivity, allowing micelles to behave as nanoreactors in which reactive species are solubilized and enhance their local concentration.

Physico-Chemical Characterization of Keratin from Wool and Chicken Feathers Extracted Using Refined Chemical Methods.

In this work, the characteristic structure of keratin extracted from two different kinds of industrial waste, namely sheep wool and chicken feathers, using the sulfitolysis method to allow film deposition, has been investigated. The structural and microscopic properties have been studied by means of scanning electron microscopy (SEM), Raman spectroscopy, atomic force microscopy (AFM), and infrared (IR) spectroscopy. Following this, small-angle X-ray scattering (SAXS) analysis for intermediate filaments has been performed. The results indicate that the assembly character of the fiber can be obtained by using the most suitable extraction method, to respond to hydration, thermal, and redox agents. The amorphous part of the fiber and medium range structure is variously affected by the competition between polar bonds (reversible hydrogen bonds) and disulfide bonds (DB), the covalent irreversible ones, and has been investigated by using fine structural methods such as Raman and SAXS, which have depicted in detail the intermediate filaments of keratin from the two different animal origins. The preservation of the secondary structure of the protein obtained does offer a potential for further application of the waste-obtained keratin in polymer films and, possibly, biocomposites.

Selective photoredox direct arylations of aryl bromides in water in a microfluidic reactor.

Carrying out photoredox direct arylation couplings between aryl halides and aryls in aqueous solutions of surfactants enables unprecedented selectivity with respect to the competing dehalogenation process, thanks to the partition coefficient of the selected sacrificial base. The use of a microfluidic reactor dramatically improves the reaction time, without eroding the yields and selectivity. The design of a metal free sensitizer, which also acts as the surfactant, sizeably improves the overall sustainability of arylation reactions and obviates the need for troublesome purification from traces of metal catalysts. The generality of the method is investigated over a range of halides carrying a selection of electron withdrawing and electron donating substituents.

Cold Crystallization of the Organic n-Type Small Molecule Semiconductor 2-Decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene S,S,S',S'-Tetraoxide.

The asymmetric n-type Ph-BTBT-C10 derivative 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene S,S,S',S'-tetraoxide is structurally investigated in the thin film regime. After film preparation by spin coating and physical vapor deposition, a rather disordered structure is observed, with a strong change of its internal degree of order upon heating. At 95 °C, a transition into a layered structure of upright standing molecules without any in-plane order appears, and at 135 °C, crystallization takes place. This phase information is combined with surface morphological studies and charge carrier mobility measurements to describe the structure and thin film transistor applicability of this molecule.

Sustainable Access to π-Conjugated Molecular Materials via Direct (Hetero)Arylation Reactions in Water and under Air.

Direct (hetero)arylation (DHA) is playing a key role in improving the efficiency and atom economy of C-C cross coupling reactions, so has impacts in pharmaceutical and materials chemistry. Current research focuses on further improving the generality, efficiency and selectivity of the method through careful tuning of the reaction conditions and the catalytic system. Comparatively fewer studies are dedicated to the replacement of the high-boiling-point organic solvents dominating the field and affecting the overall sustainability of the method. We show herein that the use of a 9:1 v/v emulsion of an aqueous Kolliphor 2 wt% solution while having toluene as the reaction medium enables the preparation of relevant examples of thiophene-containing π-conjugated building blocks in high yield and purity.

Synthesis of Conjugated Polymers by Sustainable Suzuki Polycondensation in Water and under Aerobic Conditions.

Conjugated semiconducting polymers are key materials enabling plastic (opto)electronic devices. Research in the field has a generally strong focus on the constant improvement of backbone structure and the resulting properties. Comparatively fewer studies are devoted to improving the sustainability of the synthetic route that leads to a material under scrutiny. Exemplified by the two established and commercially available luminescent polymers poly(9,9-dioctylfluorene-alt-bithiophene) (PF8T2) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (PF8BT), this work describes the first examples of efficient Suzuki-Miyaura polycondensations in water, under ambient environment, with minimal amount of organic solvent and with moderate heating. The synthetic approach enables a reduction of the E-factor (mass of organic waste/mass of product) by 1 order of magnitude, without negatively affecting molecular weight, dispersity, chemical structure, or photochemical stability of PF8T2 or PF8BT.

Preparation of Naphthalene Dianhydride Bithiophene Copolymers by Direct Arylation Polycondensation and the Latent Pigment Approach.

An alternating naphthalene dianhydride bithiophene copolymer (PNDAT2) is prepared by a combined direct arylation polycondensation and the latent pigment approach. PNDAT2 is the first reported example of an alternating conjugated polymer containing naphthalene dianhydride, the oxo-analogue of naphthalene diimide often used in electron-acceptor conjugated polymers. PNDAT2 is resistant to organic solvents and can be generated directly as film by thermal treatment of the soluble tetraester precursor PNTET2. PNDAT2 is characterized by a LUMO level of -3.9 eV, similar to that of established naphthalene diimide containing soluble copolymers. This route to insoluble electron acceptor copolymers by thermal cleavage of soluble precursors is an alternative to classical cross-linking or orthogonal processing strategies.

Preparation of Naphthalene Dianhydride Bithiophene Copolymers by Direct Arylation Polycondensation and the Latent Pigment Approach.

Invited for this month's cover are the collaborating groups of Prof. Luca Beverina from the University of Molani-Bicocca, Italy and Prof. Michael Sommer from Chemnitz University of Technology, Germany. The front cover shows the thermally induced transformation of a soluble and electron-rich naphthalene tetraester-bithiophene copolymer into the corresponding insoluble and electron-poor naphthalenetetraanhydride derivative. The combination of monochromatic squares, inspired by the work of Josef Albers, shows the color change involved in the transformation. Read the full text of the article at 10.1002/cplu.201900210.

Suzuki-Miyaura Micellar One-Pot Synthesis of Symmetrical and Unsymmetrical 4,7-Diaryl-5,6-difluoro-2,1,3-benzothiadiazole Luminescent Derivatives in Water and under Air.

The Suzuki-Miyaura cross-coupling reaction of 4,7-dibromo-5,6-difluoro-2,1,3-benzothiadiazole with different arylboronic acids can be efficiently carried out in water and under air by means of micellar coupling. The careful tuning of reaction conditions enables preparation of symmetrically and unsymmetrically substituted derivatives. The moderate to good yields obtained, along with the wide variety of available substitution patterns, makes this sustainable methodology very useful for the preparation of building blocks for luminescent optoelectronic materials.

Suzuki-Miyaura Micellar Cross-Coupling in Water, at Room Temperature, and under Aerobic Atmosphere.

Recently, oxygen-equilibrated water solutions of Kolliphor EL, a well-known surfactant, have been seen to form nanomicelles with oxygen-free cores. This has prompted the successful testing of the core environment as a green medium for palladium-catalyzed Suzuki-Miyaura cross couplings. The versatility of these conditions is endorsed by several examples, including the synthesis of relevant molecular semiconductors. The reaction medium can also be recycled, opening the way for an extremely easy and green chemistry compliant methodology.

Resistance to stress and Hc functional modulation in Liocarcinus sp.

This study is included in a project aimed to study the alterations on the structure of the Northern Adriatic Sea ecosystem produced by fishing activity. The indirect or secondary effects of fishery such as the changes of the structure and trophic relationships of the ecosystem are under investigation and we have particularly considered the effects on species such as Liocarcinus depurator that are captured and then rejected because devoid of commercial value. The objective of this study is the Liocarcinus sp. adaptative resistance to stress and the effects of biochemical parameters (allosteric effectors) on Hc functional modulation.