Direct Electrodeposition of Electrically Conducting Ni3(HITP)2 MOF Nanostructures for Micro-Supercapacitor Integration.

Micro-supercapacitors emerge as an important electrical energy storage technology expected to play a critical role in the large-scale deployment of autonomous microdevices for health, sensing, monitoring, and other IoT applications. Electrochemical double-layer capacitive storage requires a combination of high surface area and high electronic conductivity, with these being attained only in porous or nanostructured carbons, and recently found also in conducting metal-organic frameworks (MOFs). However, techniques for conformal deposition at micro- and nanoscale of these materials are complex, costly, and hard to upscale. Herein, the study reports direct, one step non-sacrificial anodic electrochemical deposition of Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2 - Ni3(HITP)2, a porous and electrically conducting MOF. Employing this strategy enables the growth of Ni3(HITP)2 films on a variety of 2D substrates as well as on 3D nanostructured substrates to form Ni3(HITP)2 nanotubes and Pt@ Ni3(HITP)2 core-shell nanowires. Based on the optimal electrodeposition protocols, Ni3(HITP)2 films interdigitated micro-supercapacitors are fabricated and tested as a proof of concept.

Targeting of M2 macrophages with IL-13-functionalized liposomal prednisolone inhibits melanoma angiogenesis in vivo.

The intricate cooperation between cancer cells and nontumor stromal cells within melanoma microenvironment (MME) enables tumor progression and metastasis. We previously demonstrated that the interplay between tumor-associated macrophages (TAMs) and melanoma cells can be disrupted by using long-circulating liposomes (LCLs) encapsulating prednisolone phosphate (PLP) (LCL-PLP) that inhibited tumor angiogenesis coordinated by TAMs. In this study, our goal was to improve LCL specificity for protumor macrophages (M2-like (i.e., TAMs) macrophages) and to induce a more precise accumulation at tumor site by loading PLP into IL-13-conjugated liposomes (IL-13-LCL-PLP), since IL-13 receptor is overexpressed in this type of macrophages. The IL-13-LCL-PLP liposomal formulation was obtained by covalent attachment of thiolated IL-13 to maleimide-functionalized LCL-PLP. C57BL/6 mice bearing B16.F10 s.c melanoma tumors were used to investigate the antitumor action of LCL-PLP and IL-13-LCL-PLP. Our results showed that IL-13-LCL-PLP formulation remained stable in biological fluids after 24h and it was preferentially taken up by M2 polarized macrophages. IL-13-LCL-PLP induced strong tumor growth inhibition compared to nonfunctionalized LCL-PLP at the same dose, by altering TAMs-mediated angiogenesis and oxidative stress, limiting resistance to apoptosis and invasive features in MME. These findings suggest IL-13-LCL-PLP might become a promising delivery platform for chemotherapeutic agents in melanoma.

The Expression of Forkhead Box P3 T Regulatory Lymphocytes as a Prognostic Factor in Malignant Melanomas.

Since transcription factor Forkhead Box P3 (FoxP3) was identified as a specific regulatory T cell (Treg) marker, researchers have scrutinized its value as a potential novel therapeutic target or a prognostic factor in various types of cancer with inconsistent results. The present analysis was performed to assess the influence of Treg FoxP3 expression on the prognosis of primary melanoma and to evaluate the correlations with various clinicopathological prognostic factors. We analyzed all eligible patients with stage pT3 primary malignant melanomas treated in a tertiary cancer center. Immunohistochemical staining for Treg FoxP3 expression was performed on retrospectively identified paraffin blocks and subsequently correlated with the outcomes of the patients. A total of 81% of the patients presented a positive Treg FoxP3 expression, being correlated with a higher risk of lymph node metastasis, tumor relapse, and death. Moreover, positive expression was statistically associated with a shorter OS. The tumor relapse rate was estimated at 36.7%. A positive expression of Treg FoxP3 and lymph node metastasis were associated with a higher risk of death based on multivariate analysis. Treg FoxP3 expression may be used as an independent prognostic factor in patients with malignant melanoma to evaluate tumor progression and survival.

Emulsion Liquid Membranes Based on Os-NP/n-Decanol or n-Dodecanol Nanodispersions for p-Nitrophenol Reduction.

Membrane materials with osmium nanoparticles have been recently reported for bulk membranes and supported composite membrane systems. In the present paper, a catalytic material based on osmium dispersed in n-decanol (nD) or n-dodecanol (nDD) is presented, which also works as an emulsion membrane. The hydrogenation of p-nitrophenol (PNP) is carried out in a reaction and separation column in which an emulsion in the acid-receiving phase is dispersed in an osmium nanodispersion in n-alcohols. The variables of the PNP conversion process and p-aminophenol (PAP) transport are as follows: the nature of the membrane alcohol, the flow regime, the pH difference between the source and receiving phases and the number of operating cycles. The conversion results are in all cases better for nD than nDD. The counter-current flow regime is superior to the co-current flow. Increasing the pH difference between the source and receiving phases amplifies the process. The number of operating cycles is limited to five, after which the regeneration of the membrane dispersion is required. The apparent catalytic rate constant (kapp) of the new catalytic material based on the emulsion membrane with the nanodispersion of osmium nanoparticles (0.1 × 10-3 s-1 for n-dodecanol and 0.9 × 10-3 s-1 for n-decanol) is lower by an order of magnitude compared to those based on adsorption on catalysts from the platinum metal group. The advantage of the tested membrane catalytic material is that it extracts p-aminophenol in the acid-receiving phase.

Two Different Tumors and Lung Aspergilloma: An Uncommon Etiopathogenic Association.

Several cases reported in the literature have confirmed the link between pulmonary aspergillosis and various malignant diseases. Furthermore, it has been observed that the correlation between carcinoid tumor and lung adenocarcinoma is quite uncommon. The etiopathogenic mechanisms underlying these correlations remain poorly defined. We present the case of a patient with three of these diseases: a lung adenocarcinoma with a lepidic pattern, a typical carcinoid, and pulmonary aspergillosis. An additional noteworthy aspect of this case pertains to the timely detection of both lung malignancies. Thus, the necessity for further investigation to ascertain the pathogenic connection among the three diseases is underscored. The ultimate objective is to enhance the prognosis of individuals diagnosed with lung cancer, which is a prevailing malignant disease on a global scale.

Laser Therapy Effects on Periodontal Status: A Randomized Study Using Gaussian Network Analysis and Structural Equation Modeling Approach.

Background and Objectives: This paper aims to assess the role of laser therapy in periodontitis through an innovative approach involving computational prediction and advanced modeling performed through network analysis (Gaussian graphical models-GGMs) and structural equations (SEM). Materials and Methods: Forty patients, exhibiting periodontal pockets with a minimum depth of 5 mm, were randomly divided into two groups: a control group and a laser group. Four specific indicators were measured for each tooth, namely periodontal pocket depth (PPD), clinical attachment level (CAL), bleeding on probing (BOP), and plaque index (PI), and the mean of six measured values was recorded at five time markers (baseline, 6 months, 1 year, 2 years, and 4 years). The assessment algorithm included enrollment, measurements, and differential non-surgical periodontal treatment, according to the group allocation. Scaling, root planing, and chlorhexidine 1% were conducted for the control group, and scaling, root planing and erbium, chromium:yttrium-scandium-gallium-garnet (Er,CR:YSGG) laser therapy were conducted for the laser group. Results: The main results highlight that the addition of laser treatment to scaling and root planing led to notable clinical improvements, decreasing the PPD values, reducing the BOP scores, and increasing the CAL. Conclusions: Notable relationships between the specific indicators considered were highlighted by both the GGMs and by SEM, thus confirming their suitability as proxies for the success of periodontal treatment.

Electrochemical Capacitance Traces with Interlayer Spacing in Two-dimensional Conductive Metal-Organic Frameworks.

Electrically conductive metal-organic frameworks (MOFs) are promising candidates for electrochemical capacitors (EC) for fast energy storage due to their high specific surface areas and potential for redox activity. To maximize energy density, traditional inorganic pseudocapacitors have utilized faradaic processes in addition to double-layer capacitance. Although conductive MOFs are usually comprised of redox active ligands which allow faradaic reactions upon electrochemical polarization, systematic studies providing deeper understanding of the charge storage processes and structure-function relationships have been scarce. Here, we investigate the charge storage mechanisms of a series of triazatruxene-based 2D layered conductive MOFs with variable alkyl functional groups, Ni3(HIR3-TAT)2 (TAT=triazatruxene; R=H, Et, n-Bu, n-Pent). Functionalization of the triazatruxene core allows for systematic variation of structural parameters while maintaining in-plane conjugation between ligands and metals. Specifically, R groups modulate interlayer spacing, which in turn shifts the charge storage mechanism from double-layer capacitance towards pseudocapacitance, leading to an increase in molar specific capacitance from Ni3(HIH3-TAT)2 to Ni3(HIBu3-TAT)2. Partial exfoliation of Ni3(HIBu3-TAT)2 renders redox active ligand moieties more accessible, and thus increases the dominance of faradaic processes. Our strategy of controlling charge storage mechanism through tuning the accessibility of redox-active sites may motivate further design and engineering of electrode materials for EC.

Controlling Charge Transport in 2D Conductive MOFs─The Role of Nitrogen-Rich Ligands and Chemical Functionality.

Two-dimensional electrically conducting metal-organic frameworks (2D-e-MOFs) have emerged as a class of highly promising functional materials for a wide range of applications. However, despite the significant recent advances in 2D-e-MOFs, developing systems that can be postsynthetically chemically functionalized, while also allowing fine-tuning of the transport properties, remains challenging. Herein, we report two isostructural 2D-e-MOFs: Ni3(HITAT)2 and Ni3(HITBim)2 based on two new 3-fold symmetric ligands: 2,3,7,8,12,13-hexaaminotriazatruxene (HATAT) and 2,3,8,9,14,15-hexaaminotribenzimidazole (HATBim), respectively, with reactive sites for postfunctionalization. Ni3(HITAT)2 and Ni3(HITBim)2 exhibit temperature-activated charge transport, with bulk conductivity values of 44 and 0.5 mS cm-1, respectively. Density functional theory analysis attributes the difference to disparities in the electron density distribution within the parent ligands: nitrogen-rich HATBim exhibits localized electron density and a notably lower lowest unoccupied molecular orbital (LUMO) energy relative to HATAT. Precise amounts of methanesulfonyl groups are covalently bonded to the N-H indole moiety within the Ni3(HITAT)2 framework, modulating the electrical conductivity by a factor of ∼20. These results provide a blueprint for the design of porous functional materials with tunable chemical functionality and electrical response.

Fluorine-free organic electrolytes for the stable electrodeposition of neodymium metal.

Electrowinning is regarded as a clean process to recover neodymium metal from secondary sources such as spent Nd-Fe-B permanent magnets, but the current methods are severely limited by a high energy consumption (molten salts), or by the high costs and environmental impact of the electrolyte components (ionic liquids). Therefore, there is a demand for more sustainable electrowinning methods for the recovery of neodymium metal. Inspired by our own previous work and the work of others, we developed new fluorine-free organic electrolytes that enable the electrodeposition of neodymium metal at room temperature. The electrolytes consist of solvated neodymium borohydride, Nd(BH4)3, dissolved in the ether solvents tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), 1,2-dimethoxyethane (DME) and diethylene glycol dimethyl ether (diglyme, G2), and these complexes can be prepared entirely from non-fluorinated precursors such as neodymium(III) chloride (NdCl3) and sodium borohydride (NaBH4). In contrast to our previous bis(trifluoromethylsulfonyl)imide-containing electrolytes, electrodeposition of neodymium proceeds over time without significant loss of current density, indicating a higher stability against unwanted side-reactions that lead to passivation of the deposit on the electrode. Characterization of the deposits by scanning electron microscopy (SEM), energy-dispersive X-ray fluorescence (EDX), and X-ray photoelectron spectroscopy (XPS) unambiguously indicated the presence of neodymium metal.

Training is not enough: child and adolescent psychiatry clinicians' impressions of telepsychiatry during the first COVID-19 related lockdown.

To ensure the continuity of care during the COVID-19 pandemic, clinicians in Child and Adolescent Psychiatry (CAP) were forced to immediately adapt in-person treatment into remote treatment. This study aimed to examine the effects of pre-COVID-19 training in- and use of telepsychiatry on CAP clinicians' impressions of telepsychiatry during the first two weeks of the Dutch COVID-19 related lockdown, providing a first insight into the preparations necessary for the implementation and provision of telepsychiatry during emergency situations. All clinicians employed by five specialized CAP centres across the Netherlands were invited to fill in a questionnaire that was specifically developed to study CAP clinicians' impressions of telepsychiatry during the COVID-19 pandemic. A total of 1065 clinicians gave informed consent and participated in the study. A significant association was found between pre-COVID-19 training and/or use of telepsychiatry and CAP clinicians' impressions of telepsychiatry. By far, the most favourable impressions were reported by participants that were both trained and made use of telepsychiatry before the pandemic. Participants with either training or use separately reported only slightly more favourable impressions than participants without any previous training or use. The expertise required to provide telepsychiatry is not one-and-the-same as the expertise that is honed through face-to-face consultation. The findings of this study strongly suggest that, separately, both training and (clinical) practice fail to sufficiently support CAP clinicians in the implementation and provision of telepsychiatry. It is therefore recommended that training and (clinical) practice are provided in conjunction.

Exosomes in Colorectal Cancer: From Physiology to Clinical Applications.

Exosomes are nanosized vesicles that have been found to be involved in many diseases. Exosomes can mediate communication between cells in a variety of ways. Certain types of mediators derived from cancer cells can play a crucial role in the development of this pathology, promoting tumor growth, invasion, metastasis, angiogenesis, and immunomodulation. Exosomes in the bloodstream show promise as a future tool for detecting cancer at an early stage. The sensitivity and specificity of clinical exosome biomarkers need to be enhanced. Knowledge of exosomes is not only important for understanding the significance of cancer progression but also for providing clinicians with useful information for the diagnosis, treatment, and discovery of methods to prevent cancer from recurring. The widespread adoption of diagnostic tools based on exosomes may revolutionize cancer diagnosis and treatment. Tumor metastasis, chemoresistance, and immunity are all aided by exosomes. A potential new approach to cancer therapy involves preventing metastasis by inhibiting miRNA intracellular signaling and blocking the formation of pre-metastatic niches. For colorectal patients, exosomes represent a promising area of investigation for improving the diagnosis, treatment, and management. Reported data demonstrate that the serum expression level of certain exosomal miRNA is significantly higher in primary colorectal cancer patients. The present review discusses mechanisms and clinical implications of exosomes in colorectal cancer.

Discovery of New Hydrazone-Thiazole Polyphenolic Antioxidants through Computer-Aided Design and In Vitro Experimental Validation.

Oxidative stress is linked to a series of diseases; therefore, the development of efficient antioxidants might be beneficial in preventing or ameliorating these conditions. Based on the structure of a previously reported compound with good antioxidant properties and on computational studies, we designed several catechol derivatives with enhanced antioxidant potential. The compounds were synthesized and physicochemically characterized, and their antioxidant activity was assessed through different antiradical, electron transfer and metal ions chelation assays, their electrochemical behavior and cytotoxicity were studied. The results obtained in the in vitro experiments correlated very well with the in silico studies; all final compounds presented very good antioxidant properties, generally superior to those of the reference compounds used. Similarly, the results obtained from studying the compounds' electrochemical behavior were in good agreement with the results of the antioxidant activity evaluation assays. Regarding the compounds' cytotoxicity, compound 7b had a dose-dependent inhibitory effect against all cell lines. In conclusion, through computer-aided design, we developed several catechol thiazolyl-hydrazones with excellent antioxidant properties, of which compound 7b, with two catechol moieties in its structure, exhibited the best antioxidant activity.

Simultaneous Determination of Steroids and NSAIDs, Using DLLME-SFO Extraction and HPLC Analysis, in Milk and Eggs Collected from Rural Roma Communities in Transylvania, Romania.

This research aims to determine five steroids and four non-steroidal anti-inflammatory drugs in milk and egg samples collected from rural Roma communities in Transylvania, Romania. Target compounds were extracted from selected matrices by protein precipitation, followed by extract purification by dispersive liquid-liquid microextraction based on solidification of floating organic droplets. The extraction procedure was optimized using a 24 full factorial experimental design. Good enrichment factors (87.64-122.07 milk; 26.97-38.72 eggs), extraction recovery (74.49-103.76% milk; 75.64-108.60% eggs), and clean-up of the sample were obtained. The method detection limits were 0.74-1.77 µg/L for milk and 2.39-6.02 µg/kg for eggs, while the method quantification limits were 2.29-5.46 µg/L for milk and 7.38-18.65 µg/kg for eggs. The steroid concentration in milk samples was

Colorectal Cancer: From Risk Factors to Oncogenesis.

Colorectal cancer is the second leading cause of cancer-related mortality worldwide. Numerous pathophysiological mechanisms, such as abnormal cell proliferation, cell differentiation, resistance to apoptosis, invasion of structures adjacent to colorectal tumor cells, and distant metastasis, are involved in colorectal carcinogenesis. These processes are initiated by the complex interaction of a number of genetic and environmental factors, including sedentary lifestyle, obesity, alcohol consumption, smoking, or gut microbiota. Despite the significant progress achieved in the diagnostic and therapeutic management of patients with colorectal cancer, there has been recently a noteworthy increase in the incidence of colorectal cancer in individuals below the age of 50 years. Early-onset colorectal cancer has a different frequency of oncogenic mutations, a higher prevalence of mucinous histology, a distinct deoxyribonucleic acid (DNA) methylation profile, a more distal location, and lower survival rates. A significant improvement in the prognosis of these patients can be achieved through the detection and removal of modifiable risk factors, along with the implementation of personalized screening strategies for individuals at high risk for this malignancy. Furthermore, gaining comprehension of the pathophysiological mechanisms by which these risk factors contribute to the process of oncogenesis may facilitate the discovery of novel therapeutic targets.

Biliary and Vascular Complications after Liver Transplantation-From Diagnosis to Treatment.

The last decades have brought impressive advances in liver transplantation. As a result, there was a notable rise in the number of liver transplants globally. Advances in surgical techniques, immunosuppressive therapies and radiologically guided treatments have led to an improvement in the prognosis of these patients. However, the risk of complications remains significant, and the management of liver transplant patients requires multidisciplinary teams. The most frequent and severe complications are biliary and vascular complications. Compared to vascular complications, biliary complications have higher incidence rates but a better prognosis. The early diagnosis and selection of the optimal treatment are crucial to avoid the loss of the graft and even the death of the patient. The development of minimally invasive techniques prevents surgical reinterventions with their associated risks. Liver retransplantation remains the last therapeutic solution for graft dysfunction, one of the main problems, in this case, being the low number of donors.

Bimetallic Anionic Organic Frameworks with Solid-State Cation Conduction for Charge Storage Applications.

A new phosphonate-based anionic bimetallic organic framework, with the general formula of A4 -Zn-DOBDP (wherein A is Li+ or Na+ , and DOBDP6- is the 2,5-dioxido-1,4-benzenediphosphate ligand) is prepared and characterized for energy storage applications. With four alkali cations per formula unit, the A4 -Zn-DOBDP MOF is found to be the first example of non-solvated cation conducting MOF with measured conductivities of 5.4×10-8  S cm-1 and 3.4×10-8  S cm-1 for Li4 - and Na4 - phases, indicating phase and composition effects of Li+ and Na+ shuttling through the channels. Three orders of magnitude increase in ionic conductivity is further attained upon solvation with propylene carbonate, placing this system among the best MOF ionic conductors at room temperature. As positive electrode material, Li4 -Zn-DOBDP delivers a specific capacity of 140 mAh g-1 at a high average discharge potential of 3.2 V (vs. Li+ /Li) with 90 % of capacity retention over 100 cycles. The significance of this research extends from the development of a new family of electroactive phosphonate-based MOFs with inherent ionic conductivity and reversible cation storage, to providing elementary insights into the development of highly sought yet still evasive MOFs with mixed-ion and electron conduction for energy storage applications.

Conjugated sulfonamides as a class of organic lithium-ion positive electrodes.

The applicability of organic battery materials in conventional rocking-chair lithium (Li)-ion cells remains deeply challenged by the lack of Li-containing and air-stable organic positive electrode chemistries. Decades of experimental and theoretical research in the field has resulted in only a few recent examples of Li-reservoir materials, all of which rely on the archetypal conjugated carbonyl redox chemistry. Here we extend the chemical space of organic Li-ion positive electrode materials with a class of conjugated sulfonamides (CSAs) and show that the electron delocalization on the sulfonyl groups endows the resulting CSAs with intrinsic oxidation and hydrolysis resistance when handled in ambient air, and yet display reversible electrochemistry for charge storage. The formal redox potential of the uncovered CSA chemistries spans a wide range between 2.85 V and 3.45 V (versus Li+/Li0), finely tunable through electrostatic or inductive molecular design. This class of organic Li-ion positive electrode materials challenges the realm of the inorganic battery cathode, as this first generation of CSA chemistries already displays gravimetric energy storage metrics comparable to those of the stereotypical LiFePO4.

Visible-Light Augmented Lithium Storage Capacity in a Ruthenium(II) Photosensitizer Conjugated with a Dione-Catechol Redox Couple.

Controlling redox activity of judiciously appended redox units on a photo-sensitive molecular core is an effective strategy for visible light energy harvesting and storage. The first example of a photosensitizer - electron donor coordination compound in which the photoinduced electron transfer step is used for light to electrical energy conversion and storage is reported. A photo-responsive Ru-diimine module conjugated with redox-active catechol groups in [Ru(II)(phenanthroline-5,6-diolate)3 ]4- photosensitizer can mediate photoinduced catechol to dione oxidation in the presence of a sacrificial electron acceptor or at the surface of an electrode. Under potentiostatic condition, visible light triggered current density enhancement confirmed the light harvesting ability of this photosensitizer. Upon implementation in galvanostatic charge-discharge of a Li battery configuration, the storage capacity was found to be increased by 100 %, under 470 nm illumination with output power of 4.0 mW/cm-2 . This proof-of-concept molecular system marks an important milestone towards a new generation of molecular photo-rechargeable materials.

Common peroneal nerve palsy after primary total hip arthroplasty.

PURPOSE: The study wants to evaluate the incidence, the clinical evolution, and treatment of common peroneal nerve (CPN) palsy after primary total hip arthroplasty. METHODS: Our clinical prospective study was made between January 2016 and December 2020. The study group comprised 1240 total hip replacements over a period of five years. Six cases were diagnosed with CPN palsy (0.48%). Five were women and one man, aged from 52 to 71 years old. The common peroneal nerve lesion was diagnosed clinically and by electromyography. RESULTS: The follow-up period was at least 24 months post-operatively. In all six cases, there was a complete common peroneal nerve palsy, documented by electromyography. The poorest results were obtained in the older patients and those who had the highest body mass index, which at two years post-operatively achieved only a partial sensory rehabilitation, with complete motor deficit. All patients can walk unassisted, without support, with one case having complete rehabilitation achieved 18 months postoperatively and three with partial rehabilitation. CONCLUSION: CPN palsy after primary THA is a very serious complication with poor functional outcome. There is no consensus regarding the treatment. The age and the intensity of the rehabilitation program are the only significant factors for the medical rehabilitation after this debilitating post-operative complication.

Strategies for Improving Bioavailability, Bioactivity, and Physical-Chemical Behavior of Curcumin.

Curcumin (CCM) is one of the most frequently explored plant compounds with various biological actions such as antibacterial, antiviral, antifungal, antineoplastic, and antioxidant/anti-inflammatory properties. The laboratory data and clinical trials have demonstrated that the bioavailability and bioactivity of curcumin are influenced by the feature of the curcumin molecular complex types. Curcumin has a high capacity to form molecular complexes with proteins (such as whey proteins, bovine serum albumin, ß-lactoglobulin), carbohydrates, lipids, and natural compounds (e.g., resveratrol, piperine, quercetin). These complexes increase the bioactivity and bioavailability of curcumin. The current review provides these derivatization strategies for curcumin in terms of biological and physico-chemical aspects with a strong focus on different type of proteins, characterization methods, and thermodynamic features of protein-curcumin complexes, and with the aim of evaluating the best performances. The current literature review offers, taking into consideration various biological effects of the CCM, a whole approach for CCM-biomolecules interactions such as CCM-proteins, CCM-nanomaterials, and CCM-natural compounds regarding molecular strategies to improve the bioactivity as well as the bioavailability of curcumin in biological systems.