Sequence matters: Total body irradiation (TBI)-based myeloablative conditioning with post-transplant cyclophosphamide may reduce the early nonrelapse mortality compared with pretransplant cyclophosphamide plus TBI.

OBJECTIVES: High-dose total body irradiation (TBI) is considered a cornerstone of myeloablative conditioning for allogeneic stem cell transplantation (allo-SCT). We retrospectively compared the main outcomes of an HLA matched or 1-allele mismatched related or unrelated allo-SCT in adult patients affected by acute leukemia (AL) or myelodysplastic syndromes (MDS). METHODS: Fifty-nine patients received cyclophosphamide (Cy)-TBI (13.5 Gy) and graft-versus-host disease (GVHD) prophylaxis with a calcineurin-inhibitor plus methrotrexate (CyTBI group) and 28 patients received fludarabine-TBI (8.8-13.5 Gy) and GVHD prophylaxis with PTCy and tacrolimus (FluTBI-PTCy group). RESULTS: Median follow-up for survivors was 82 and 22 months. The 12-month probability of overall survival and progression-free survival were similar (p = .18, p = .7). The incidence of Grades 2-4 and 3-4 acute GVHD, and the incidence of moderate-to-severe chronic GVHD were higher in the CyTBI group (p = .02, p < .01and p = .03). Nonrelapse mortality (NRM) at 12 months posttransplant was higher in the CyTBI group (p = 0.05), while the incidence of relapse was similar in both groups (p = 0.7). The number of GVHD-free and relapse-free patients without systemic immunosuppression (GRFS) at 1-year posttransplant was higher in the FluTBI-PTCy group (p = 0.01). CONCLUSIONS: The study confirms the safety and efficacy of a novel FluTBI-PTCy platform with reduced incidence of severe acute and chronic GVHD, and early improvement of NRM.

Developing Green Innovations in the Wine Industry: An Applied Analysis.

Winemaking is an ancestral activity characterized by its strong roots in the culture, heritage, and people of the producing regions. In addition to providing important health benefits, wine is a product that is widely accepted by society. However, the socioeconomic context is evolving at a rapid pace, and new requirements and needs are forcing companies to innovate in order to remain competitive in the markets, especially in terms of sustainability. The main aim of this paper is to analyze the relationship between green transformational leadership and green innovation, as well as the mediating effect of green motivation and green creativity in this relationship. Data were obtained from a sample of 196 Spanish companies belonging to the wine industry and, as a method of analysis, was used partial least squares structural equation modeling PLS-SEM. The results show a positive and significant relationship between green transformational leadership and green innovation in wine companies. Furthermore, green motivation and green creativity exert a mediating effect in this relationship. It is concluded that the managers of wine companies should encourage employee motivation and creativity, especially in ecological terms, by creating an environment conducive to the development of environmentally friendly innovations.

Perforator Flaps Covering Alloplastic Materials in Full-Thickness Chest Wall Defects Reconstruction: A Safe Option?

Large full-thickness chest wall reconstruction requires an alloplastic material to ensure chest wall stability, as well as a flap that provides good soft-tissue coverage. The choice not to use perforator flaps over any mesh or inert material is often based on the concern that the vascularization would be inadequate. However, perforator flaps have shown good results in several reconstructive fields, minimizing donor-site morbidity and offering versatility when local tissues are unavailable or affected by radiotherapy. In this study, we present 4 cases of patients with full-thickness chest wall defects that were repaired with a double Marlex mesh, acrylic cement (n = 2) or a double patch of Goretex (n = 2) in combination with perforator flaps (3 deep inferior epigastric artery perforators and 1 lumbar artery perforator flap). The results we obtained are encouraging, and we believe the use of perforator flaps in combination with alloplastic materials should be considered as a reliable option for full-thickness chest wall defect reconstruction.

Anomeric effect in halogenated methanols: a quantum theory of atoms in molecules study.

The quantum theory of atoms in molecules (QTAIM) has been used to analyze the gauche conformational preference of fluoromethanol and chloromethanol. The analysis of the total atomic population and localization and delocalization indices show trends that are not in line with the hyperconjugative explanation. Energy terms arising from the QTAIM partitioning have been obtained for fluoromethanol, revealing that (i) C-O interaction plays the most significant role in stabilizing the gauche rotamer and (ii) the summation of exchange terms (the only ones that could be related to hyperconjugation) has a smaller weight than electrostatic ones in the energy balance among gauche, anti, and syn conformations; however, they are far from being negligible.

Comparison of hemihypoglossal-facial nerve transposition with a cross-facial nerve graft and muscle transplant for the rehabilitation of facial paralysis using the facial clima method.

To compare quantitatively the results obtained after hemihypoglossal nerve transposition and microvascular gracilis transfer associated with a cross facial nerve graft (CFNG) for reanimation of a paralysed face, 66 patients underwent hemihypoglossal transposition (n = 25) or microvascular gracilis transfer and CFNG (n = 41). The commissural displacement (CD) and commissural contraction velocity (CCV) in the two groups were compared using the system known as Facial clima. There was no inter-group variability between the groups (p > 0.10) in either variable. However, intra-group variability was detected between the affected and healthy side in the transposition group (p = 0.036 and p = 0.017, respectively). The transfer group had greater symmetry in displacement of the commissure (CD) and commissural contraction velocity (CCV) than the transposition group and patients were more satisfied. However, the transposition group had correct symmetry at rest but more asymmetry of CCV and CD when smiling.

Electronic interpretation of conformational preferences in benzyl derivatives and related compounds.

Quantum Theory of Atoms in Molecules (QTAIM) analysis on B3LYP/6-311++G(2d,2p) 6d electron densities of five benzyl derivatives (C(6)H(5)-CH(2)X; X = F, Cl, OH, SH, NH(2)) and seven related fluorides of furan, pyrrole, and naphthalene indicates that the preference for perpendicular or gauche conformation exhibited by these compounds is related to the diminution of the steric repulsion between the heteroatom at the substituent and the closest hydrogen in the ring. The electron density reorganization can be satisfactorily explained on the basis of these repulsive interactions, while no evidence of larger hyperconjugative delocalization is observed in the preferred conformations.

Influence of the solvent on the charge distribution of anomeric compounds.

Conformational preferences of methanediol, dimethoxymethane, methanediamine, and fluoromethanol in the presence of solvents of diverse polarity (water, acetone, and chloroform), modeled with the polarizable continuum model, were analyzed within the framework of the Quantum Theory of Atoms in Molecules. The results indicate that the hydrogens bonded to the anomeric carbon experience the largest reorganization of electron density upon conformational change, as was obtained from previous calculations in the gas phase. When the water solvation is simulated by explicit inclusion of water molecules, the electron density reorganization involved in the cluster formation is significantly different for each conformer of methanediol. As a consequence, similar depletions of electron population are displayed by the hydrogens of hydroxyl and methylene groups in the cluster obtained for the most stable conformer of methanediol, with regard to that built for the completely antiperiplanar conformer.

Interpretation of anomeric effect in the N-C-N unit with the quantum theory of atoms in molecules.

The conformational preferences of six model compounds for the N-C-N anomeric unit (methanediamine, 2,2-propanediamine, N,N,N',N'-tetramethyl-methanediamine, 1,3-dizacyclohexane, 1,3,5-triazacyclohexane, and 2-aminopiperidine) were analyzed within the framework of the Quantum Theory of Atoms in Molecules. The relative stabilization of the conformers is related to two factors: (i) the reduction of the electron population experienced by the hydrogens of the central methylene when they display more gauche arrangements to lone pairs (lp) and (ii) the reduction of the electron population of aminic hydrogens when the corresponding N-H bond is in a parallel arrangement to the lone pair of another N. The former depletion takes place in lp-N-C-N antiperiplanar dispositions, whereas the latter is shown in lp-N-C-N gauche arrangements. Therefore, we can say that the electron density removed from the central hydrogens is moved to an aminic one on going from an antiperiplanar to a gauche disposition of a lp-N-C-N unit. The relative energies of aminic and central hydrogens in the conformer series is the main factor determining the conformational preference. In contrast to what happens in O-C-O containing compounds (where both N(H) depletions take place in the O-C-O-H gauche dispositions), the stabilization gained by N and C atoms plays a secondary role. This is in line with a general trend exhibited by hydrogens as the most available (less energy cost) atomic basins for receiving or providing electron density along a chemical change. It also explains why the anomeric conformational stabilization due to the N-C-N units is significantly less than that of the O-C-O- units. Moreover, the variations of electron population due to conformational changes are not in keeping with the stereoelectronic model of the anomeric effect, as was previously found for diverse molecules containing the O-C-O anomeric unit.

Atoms in molecules interpretation of the anomeric effect in the O--C--O unit.

The conformational preferences of two model compounds for the O--CH2--O anomeric unit: methanediol and dimethoxymethane analyzed within the framework of the QTAIM theory provide a new interpretation of the anomeric effect. The characteristic stabilization of the gauche conformers of these compounds is accompanied by a progressive reduction of the electron population of the hydrogens of the central methylene as the number of their gauche interactions to lone pairs rises. The electron population removed from these atoms during the conformational change is gained in the gauche conformers by atoms of larger atomic number, which results in a more negative molecular energy. Also, the variations displayed by atomic populations and the QTAIM delocalization indexes are not keeping in line with the hyperconjugative model of the anomeric effect.

On the electronic origin of strain energy: QTAIM study of perfluorocycloalkanes.

The strain energies (SE) of the five smallest perfluorocycloalkanes (c-CnF2n; n=3, 4, 5, 6, and 7) were calculated by means of several homodesmotic processes using B3LYP/6-31++G(d,p) optimized molecular energies. These values were compared with the energy difference between the linear and cyclic CF2 groups calculated by means of the quantum theory of atoms in molecules (QTAIM) applied on charge densities obtained at the same computational level. The differences between the values computed with both methods vary from 255 (n=3) to 629 (n=7) kJ mol-1. These differences arise because QTAIM-computed SE contain the energy involved in opening the ring to give rise to nearly transferable central CF2 fragments of linear perfluoroalkanes, whereas homodesmotic energies contain energy terms corresponding to transformation of nontransferable linear CF2 fragments and a ring-opening energy, which depending on the process, transforms CF2 cyclic compounds into nearly transferable or nontransferable linear CF2 groups.

Quantum theory of atoms in molecules analysis on the conformational preferences of vinyl alcohol and related ethers.

Vinyl alcohol, methyl vinyl ether, and tert-butyl vinyl ether were studied within the framework of the quantum theory of atoms in molecules at the B3LYP/6-311++G(2d,2p) level. Local and integrated properties of the charge density indicate that the anti conformational preference of the tert-butyl derivative is not due to a differing resonance contribution with regard to the less bulky vinyl ethers but to steric effects. There is a small delocalization of charge density, either total or pi, between oxygen and the terminal vinyl carbon, which does not support the resonance picture of vinyl compounds.