The prognostic-nutritional index in HPV-negative head and neck squamous cell carcinoma treated with upfront surgery: a multi-institutional series

Objectives: To evaluate the prognostic value of pre-treatment prognostic-nutritional index (PNI) in patients with HPV-negative head and neck squamous cell carcinoma (HNSCC). Methods: A multi-institutional retrospective series of HPV-negative, Stages II-IVB, HNSCCs treated with upfront surgery was evaluated. Correlation of pre-operative blood markers and PNI with 5-year overall (OS) and relapse-free (RFS) survival was tested using linear and restricted cubic spline models, as appropriate. The independent prognostic effect of patient-related features was assessed with multivariable models. Results: The analysis was conducted on 542 patients. PNI ≥ 49.6 (HR = 0.52; 95% CI, 0.37-0.74) and Neutrophil-to-Lymphocyte Ratio (NLR) > 4.2 (HR = 1.58; 95% CI, 1.06-2.35) confirmed to be independent prognosticators of OS, whereas only PNI ≥ 49.6 (HR = 0.44; 95% CI, 0.29-0.66) was independently associated with RFS. Among pre-operative blood parameters, only higher values of albuninaemia and lymphocyte count (> 1.08 x 103/microL), and undetectable basophile count (= 0 103/microL) were independently associated with better OS and RFS. Conclusions: PNI represents a reliable prognostic tool providing an independent measure of pre-operative immuno-metabolic performance. Its validity is supported by the independent prognostic role of albuminaemia and lymphocyte count, from which it is derived

Prognostic value of H-index in patients surgically treated for squamous cell carcinoma of the larynx.

OBJECTIVE: Recently, a novel host-related index, the Host-index (H-index), including both inflammatory and nutritional markers, has been described and observed to stratify prognosis in patients with squamous cell carcinoma (SCC) of the oral cavity more accurately than other host-related indexes This study aimed to investigate the prognostic performance of the H-index using pretreatment blood tests in patients receiving up-front surgery for SCC of the larynx. METHODS: This retrospective observational study included a multicenter series of consecutive patients with SCC of the larynx diagnosed between 1 January 2009 and 31 July 2018, whose pretreatment blood tests were available and included the parameters necessary for the calculation of neutrophil to lymphocyte ratio (NLR) and the H-index. Their association with disease-free survival (DFS) and overall survival (OS) was measured. RESULTS: A total of 231 patients were eligible for the present analysis (median [range] age, 68 [37-96] years; 191 [82.7%] men). The median follow-up was 73 months. In multivariable Cox proportional hazards regression models, increasing age (adjusted hazard ratio [aHR], 1.07 per year; 95% CI, 1.04-1.09), advanced pT stage (aHR = 1.71 95% CI: 1.07-2.71), and having close or positive surgical margins (aHR = 2.01; 95% CI: 1.21-3.33) were significantly associated with poor OS. Among blood parameters, a higher neutrophil count was a strong predictor of both worse DFS (aHR for recurrence/death = 2.34; 95% CI: 1.24-4.40) and OS (aHR for death = 2.67; 95% CI: 1.51-4.71). Among inflammatory blood indexes, while NLR was not significantly associated with DFS or OS, patients with H-index ≥8.37 showed a higher aHR for both recurrence/death (2.82; 95% CI: 1.65-4.79) and death (2.22; 95% CI: 1.26-3.89). CONCLUSION: In conclusion, the present study confirms the prognostic value of pretreatment H-index, an easily measurable inflammatory and nutritional index, in patients with SCC of the larynx. LEVEL OF EVIDENCE: III

From Nanoparticles to Non-Covalent Interactions : : Electron Transfer in Inorganic Supramolecular Mixed Valence Systems

Understanding the intricacies of inner sphere electron transfer has been a challenge for nearly 50 years. Since the preparation of the Creutz-Taube ion extensive research in inorganic mixed valence systems has been performed. We employ coalescence of [nu](CO) bandshapes observed in the 1-D infrared (IR) spectra of mixed valence complexes to determine rate constants of electron transfer (ET). Herein we report synthesis, characterization, and spectroscopy of Ru₃O clusters bound to metallic nanoparticles, and report ET rates in the "ultrafast" regime. We observe that ET rates are faster when there is favorable electronic alignment between the Ru clusters and the Au nanoparticle. In addition, results show that ground state ET rate constants that are in the "ultrafast" regime depend on the pre-exponential term within the frequency factor, [nu]N not the activation energy as expected in a system undergoing ergodic electron transfer. We extended our knowledge of these complexes by studying ET at a semiconducting nanoparticle interface. Working in collaboration with Prof. Emily Weiss at Northwestern University, a complementary view of the parameters that govern ET in such systems has been developed by investigating ET rates between the triruthenium clusters and QDs. The photoinduced electron transfer rate from photoexcited CdSe QDs to triruthenium clusters having either a pyridine-4-carboxylic acid or a 4- mercaptopyridine linkage are reported. Results show that the intrinsic charge separation rate constant (kCS,int), is approximately seven times faster for a thiol linked cluster compared to a nicotinic acid bound cluster. Thus the charge transfer rates between colloidal quantum dots and redox-active ligands adsorbed to their surfaces can be tuned through the choice of the coordinating headgroup of the ligand. We report that exchange of electrons across hydrogen bonds can increase the strength of typically weak interactions. A thermodynamically stable mixed valence dimer is obtained upon the one electron reduction of a Ru₃O cluster with a isonicotinic acid ancillary ligand. Observed intervalence charge transfer bands (IVCT) indicate significant coupling between the two Ru centers through linked by a hydrogen bonding interaction. The IVCT bands are found to be best explained by a semi-classical 3 -state model, further highlighting the importance of the bridging interaction in these systems. Additionally, we report that the electronic coupling between two metal centers can be modulated by simple ancillary ligand substitution. The wavefunction overlap of two metal centers bridged by a hydrogen bond is found to be non- zero. We report a series of new Ru₃O clusters with ancillary ligands capable of pi-stacking in solution upon a single electron reduction. Large splittings are observed berween the reductions in the electrochemical responses of these newly synthesized systems. The effects on the electrochemical splitting of the reduction waves by donating and withdrawing ligands on the "bridge" are compared. A crystal structure of the ground state shows no significant evidence of pi-pi interaction between clusters in solution. The major themes of this thesis are the role of electronic coupling, Hab, on long range ET in supramolecular mixed valence systems, and the importance of the bridging interaction in modulating Hab in these system

Ultrafast Electron Transfer Across a Gold Nanoparticle: A Study of Ancillary Ligand and Solvent Influences

Supramolecular mixed valence assemblies exhibiting picosecond rates of electron transfer are reported. Trinuclear ruthenium clusters of the type [Ru₃O­(OAc)₆(CO)­(L)­(pyS)], where L = 4-cyanopyridine, pyridine, and 4-dimethylaminopyridine, bound to Au nanoparticles (NPs) are electrochemically reduced to form mixed valence nanoclusters. Infrared spectroelectrochemical responses show dynamic coalescence of the ν­(CO) region, indicating that electron transfer (ET) between Ru clusters attached via a π-conjugated bridge to the NPs occurs on the vibrational time scale. Bloch simulation of IR ν­(CO) spectra gives <i>k</i>_et on the order of 10¹¹–10¹² s^–1. Ground state electron transfer rates exhibit a strong dependence on solvent dynamics. Results suggest that solvent dynamics control electron transfer, while solvent reorganization energy, λ_s, is apparently not influencing ET rates. This behavior is consistent with supramolecular mixed valence assemblies that lie on the nearly barrierless, Class II/III borderline of mixed valency

Surgical Navigation in Mandibular Reconstruction: Accuracy Evaluation of an Innovative Protocol

Aim: the purpose of this work is to present an innovative protocol for virtual planning and surgical navigation in post-oncological mandibular reconstruction through fibula free flap. In order to analyze its applicability, an evaluation of accuracy for the surgical protocol has been performed. Methods: 21 patients surgically treated for mandibular neoplasm have been included in the analysis. The Brainlab Vector Vision 3.0&reg; software for surgical navigation has been used for preoperative surgical planning and intra-operative navigation. A post-operative accuracy evaluation has been performed matching the position of mandibular landmarks between pre-operative and post-operative CT scans. Results: the maximal discrepancy observed was included between &minus;3.4 mm and +3.2 mm, assuming negative values for under correction and positive values for overcorrection. An average grade of accuracy included between 0.06 &plusmn; 0.58 mm and 0.43 &plusmn; 0.68 mm has been observed for every mandibular landmark examined, except for mandibular angles that showed a mean discrepancy value included between 1.36 &plusmn; 1.73 mm and 1.46 &plusmn; 1.02 mm when compared to preoperative measurements. Conclusion: a satisfying level of accuracy has been observed in the protocol presented, which appears to be more versatile if compared to closed custom-made systems. The technique described may represent a valid option for selected patients, but it cannot be considered for routine activity because of the complexity of the method, the mobility of the jaw, the necessity of surgical navigator and the long surgical learning curve that is required

The Comprehensive Facial Injury (CFI) Score Is an Early Predictor of the Management for Mild, Moderate and Severe Facial Trauma

Identifying groups of patients with homogeneous characteristics and comparable outcomes improves clinical activity, patients&rsquo; management, and scientific research. This study aims to define mild, moderate, and severe facial trauma by validating two cut-off values of the Comprehensive Facial Injury (CFI) score and describing their foreseeable clinical needs to create a useful guide in patient management, starting from the first evaluation. The individual CFI score, overall surgical time, and length of hospitalization are calculated for a sample of 1400 facial-injured patients. Receiver Operating Characteristic (ROC) analysis and the corresponding Area Under the Curve (AUC) is tested, and a CFI score &ge;4 is selected to discriminate patients undergoing surgical management under general anesthesia (Positive Predictive Value, PPV of 91.4%), while a CFI score &ge;10 is selected to identify patients undergoing major surgical procedures (Negative Predictive Value, NPV of 91.7%). These results are enhanced by the consensual trend of Length of Stay outcome. The use of the CFI score allows us to distinguish between the &ldquo;Mild facial trauma&rdquo; with a low risk of hospitalization for surgical treatment, the &ldquo;Moderate facial trauma&rdquo; with a high probability of surgical treatment, and the &ldquo;Severe facial trauma&rdquo; that requires long-lasting surgery and hospital stay, with an increased incidence of Intensive Care Unit admission

Tuning Electron Delocalization and Transfer Rates in Mixed-Valent Ru₃O Complexes through “Push–Pull” Effects

Electron transfer rates in a series of oxo-centered triruthenium clusters featuring an extended aromatic ancillary ligand of the type [Ru₃(OAc)₆(μ₃-O)­(CO)­(L)­(pep)], where L = 4-cyanopyridine (cpy), pyridine (py), or 4-(dimethylamino)­pyridine (dmap) and pep = 4-(phenylethynyl)­pyridine were investigated. The electron self-exchange rate constants for the 0/– couple were determined by ¹H NMR line broadening experiments and found to range from 4.3 to 9.2 (× 10⁷ M^–1 s^–1) in deuterated acetonitrile (ACN-<i>d</i>₃). Relative rates of self-exchange can be rationalized on the basis of increased contact area between self-exchanging pairs, and a push–pull modulation of electron density between the pep vs ancillary pyridine ligands. Faster self-exchange was observed with increasing electron-donating character of the ancillary pyridine ligand substituent (dmap > py > cpy), and this was attributed to increased orbital overlap between self-exchanging pairs. These results are supported by trends observed in ¹H NMR contact shifts of the pep ligand that were found to depend on the electron-donating or -withdrawing nature of the ancillary pyridine ligand

Effectiveness of Resective Surgery in Complex Ameloblastoma of the Jaws: A Retrospective Multicenter Observational Study

Ameloblastoma is a rare, benign, odontogenic tumor of epithelial origin, characterized by locally aggressive, expansive growth. Treatment is controversial due to the risk of relapse. The aim of this multicenter retrospective study was to evaluate the effectiveness of complete resection in cases of complex ameloblastoma, which is considered at a higher risk of recurrence. Patients who met at least one of these criteria were included: recurrence, soft-tissue involvement, complete erosion of internal/external cortical walls with involvement of the inferior margin of the mandible, and invasion of the maxillary sinus or nasal cavity. Demographic data, tumor site, type of surgery, histological features, and follow-up information were collected for each patient. The cohort included 55 patients with a mean follow-up of 108 &plusmn; 66 months. A multivariate logistic model was used to evaluate variables independently associated with relapse. There were six soft-tissue or maxillary sinus relapses, with a recurrence rate of 10.9%. Most of them arose in patients previously treated. The statistical analysis identified the maxillary location as a fundamental relapse risk factor. En bloc resection with large surgical safety margins seemed to be effective in preventing the relapses. However, complete resection was less effective in preventing recurrences in the soft tissues or maxillary sinus