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The purpose of the present study was to analyze the attacking tasks and tactical organization of elite Women's Water Polo. The sample consisted of 442 attack sequences of 8 games played by the top teams in a European Championship. Seventeen variables were analyzed according to the position and player's participation, tactical organization and playing styles, as well as the efficacy of actions performed. The results from this study indicate that positional attack was the predominant performance factor in the attacking process. To this occurrence, the mixed floating defense was identified as the most frequent opposition. The counter-attack proved to be the most efficient strategy. The attacking process frequently started by ball recovering, in anticipation, and by the defense of the goal-keeper in the 2m zone. In central path, a first long-range pass to the right wing predominated. Teams preferred spontaneous shot on goal supported by assisted displacements, and extra player man offence situations. In general, the attacking sequences, do not take longer than 35s to be developed.) Teams efficiency emerged related to the tactical means adopted, namely the spontaneous shot at goal on the front line and numerical superiority of players in attacking game situations. [ABSTRACT FROM AUTHOR]

Controlled synthesis of phase-pure metal-organic frameworks (MOFs) is essential for their application in technological areas such as catalysis or gas sorption. Yet, knowledge of their phase formation and growth remain rather limited, particularly with respect to species such as water whose vital role in MOF synthesis is often neglected. As a consequence, synthetic protocols often lack reproducibility when multiple MOFs can form from the same metal source and linker, and phase mixtures are obtained with little or no control over their composition. In this work, the role of water in the formation of the Zr-porphyrin MOF disordered PCN-224 (dPCN-224) is investigated. Through X-ray total scattering and scanning electron microscopy, it is observed that dPCN-224 forms via a metal-organic intermediate that consists of Zr 6 O 4 (OH) 4  clusters linked by tetrakis(4-carboxy-phenyl)porphyrin molecules. Importantly, water is not only essential to the formation of Zr 6 O 4 (OH) 4  clusters, but it also plays a primary role in dictating the formation kinetics of dPCN-224. This multidisciplinary approach to studying the speciation of dPCN-224 provides a blueprint for how Zr-MOF synthesis protocols can be assessed and their reproducibility increased, and highlights the importance of understanding the role of water as a decisive component in Zr-MOF formation., (© 2023 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

Several metal-organic frameworks (MOFs) excel in harvesting water from the air or as heat pumps as they show a steep increase in water uptake at 10-30 % relative humidity (RH%). A precise understanding of which structural characteristics govern such behavior is lacking. Herein, CAU-10-H and CAU-10-CH 3 are studied with H, CH 3 corresponding to the functions grafted to the organic linker. CAU-10-H shows a steep water uptake ≈18 RH% of interest for water harvesting, yet the subtle replacement of H by CH 3 in the organic linker drastically changes the water adsorption behavior to less steep water uptake at much higher humidity values. The materials' structural deformation and water ordering during adsorption with in situ sum-frequency generation, in situ X-ray diffraction, and molecular simulations are unraveled. In CAU-10-H, an energetically favorable water cluster is formed in the hydrophobic pore, tethered via H-bonds to the framework μOH groups, while for CAU-10-CH 3 , such a favorable cluster cannot form. By relating the findings to the features of water adsorption isotherms of a series of MOFs, it is concluded that favorable water adsorption occurs when sites of intermediate hydrophilicity are present in a hydrophobic structure, and the formation of energetically favorable water clusters is possible., (© 2023 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

Titanium-based metal-organic framework, NH 2 -MIL-125(Ti), has been widely investigated for photocatalytic applications but has low activity in the hydrogen evolution reaction (HER). In this work, we show a one-step low-cost postmodification of NH 2 -MIL-125(Ti) via impregnation of Co(NO 3 ) 2 . The resulting Co@NH 2 -MIL-125(Ti) with embedded single-site Co II species, confirmed by XPS and XAS measurements, shows enhanced activity under visible light exposure. The increased H 2 production is likely triggered by the presence of active Co I transient sites detected upon collection of pump-flow-probe XANES spectra. Furthermore, both photocatalysts demonstrated a drastic increase in HER performance after consecutive reuse while maintaining their structural integrity and consistent H 2 production. Via thorough characterization, we revealed two mechanisms for the formation of highly active proton reduction sites: nondestructive linker elimination resulting in coordinatively unsaturated Ti sites and restructuring of single Co II sites. Overall, this straightforward manner of confinement of Co II cocatalysts within NH 2 -MIL-125(Ti) offers a highly stable visible-light-responsive photocatalyst.

The outstanding diversity of Zr-based frameworks is inherently linked to the variable coordination geometry of Zr-oxo clusters and the conformational flexibility of the linker, both of which allow for different framework topologies based on the same linker-cluster combination. In addition, intrinsic structural disorder provides a largely unexplored handle to further expand the accessibility of novel metal-organic framework (MOF) structures that can be formed. In this work, we report the concomitant synthesis of three topologically different MOFs based on the same M 6 O 4 (OH) 4 clusters (M = Zr or Hf) and methane-tetrakis( p -biphenyl-carboxylate) (MTBC) linkers. Two novel structural models are presented based on single-crystal diffraction analysis, namely, cubic c-(4,12)MTBC-M 6 and trigonal tr-(4,12)MTBC-M 6 , which comprise 12-coordinated clusters and 4-coordinated tetrahedral linkers. Notably, the cubic phase features a new architecture based on orientational cluster disorder, which is essential for its formation and has been analyzed by a combination of average structure refinements and diffuse scattering analysis from both powder and single-crystal X-ray diffraction data. The trigonal phase also features structure disorder, although involving both linkers and secondary building units. In both phases, remarkable geometrical distortion of the MTBC linkers illustrates how linker flexibility is also essential for their formation and expands the range of achievable topologies in Zr-based MOFs and its analogues.

A novel synthetic approach is described for the targeted preparation of multivariate metal-organic frameworks (MTV-MOFs) with specific combinations of metal elements. This methodology is based on the use of molecular complexes that already comprise desired metal-atom combinations, as building units for the MTV-MOF synthesis. These units are transformed into the MOF structural constituents through a ligand/linker exchange process that involves structural modifications while preserving their originally encoded atomic combination. Thus, through the use of heterometallic ring-shaped molecules combining gallium and nickel or cobalt, we have obtained MOFs with identical combinations of the metal elements, now incorporated in the rod-shaped secondary building unit, as confirmed with a combination of X-ray and electron diffraction, electron microscopy, and X-ray absorption spectroscopy techniques.

The chemistry of metal-organic and covalent organic frameworks (MOFs and COFs) is perhaps the most diverse and inclusive among the chemical sciences, and yet it can be radically expanded by blending it with nanotechnology. The result is reticular nanoscience, an area of reticular chemistry that has an immense potential in virtually any technological field. In this perspective, we explore the extension of such an interdisciplinary reach by surveying the explored and unexplored possibilities that framework nanoparticles can offer. We localize these unique nanosized reticular materials at the juncture between the molecular and the macroscopic worlds, and describe the resulting synthetic and analytical chemistry, which is fundamentally different from conventional frameworks. Such differences are mirrored in the properties that reticular nanoparticles exhibit, which we described while referring to the present state-of-the-art and future promising applications in medicine, catalysis, energy-related applications, and sensors. Finally, the bottom-up approach of reticular nanoscience, inspired by nature, is brought to its full extension by introducing the concept of augmented reticular chemistry. Its approach departs from a single-particle scale to reach higher mesoscopic and even macroscopic dimensions, where framework nanoparticles become building units themselves and the resulting supermaterials approach new levels of sophistication of structures and properties.

Due to the growing engagement of youth in water polo practice, we aimed to characterize age-grouped players across anthropometric, general and specific motor abilities and contextual domains. We have also examined the associations of players' specific skills with their anthropometric and general motor characteristics. One-hundred-and-one male water polo players, grouped into 12-, 13- and 14-year age cohorts were recruited. One-way ANOVA explained age-cohort variance, and a multiple linear regression was used to assess the association between variables. The variance in cohorts was explained by arm span (25%), stature, hand breadth and length (17%) fat-free mass (18%), 20 m sprint (16%), sit-ups (18%), medicine ball throw (27%), anaerobic (31%) and aerobic performance (21%), change of direction (18%), and in-water vertical jump (14%). The variance of in-water vertical jump, 10 m sprint, change of direction and aerobic fitness for players' anthropometric characteristics were, 32, 25, 14 and 10% (respectively). The players' upper-limb explosive power explained 30, 22 and 17% of variance for in-water vertical jump, 10 m sprint and aerobic fitness, respectively. Body mass had an inverse, and arm span had a direct association with in-water vertical jump and swim velocity capability, arm span had an inverse and direct association with change of direction and aerobic fitness, respectively. The upper limbs' explosive power related directly to in-water vertical jump and aerobic fitness skills, but inversely with 10 m sprint scores.

Molecular sieving membranes with uniform pore size are highly desired for carbon dioxide separation. All-silica zeolite membranes feature well-defined micropores, but the size-exclusion effect is significantly compromised by the non-selective macro-pores generated during detemplation. Here we propose a template modulated crystal transition (TMCT) approach to tune the flexibility of Decadodecasil 3 R (DD3R) zeolite to prepare ultra-selective membranes for CO 2 /CH 4 separation. An instantaneous overheating is applied to synchronize the template decomposition with the structure relaxation. The organic template molecules are transitionally converted to tight carbon species by the one-minute overheating at 700 °C, which are facilely burnt out by a following moderate thermal treatment. The resulting membranes exhibit CO 2 /CH 4 selectivity of 157~1,172 and CO 2 permeance of (890~1,540) × 10 -10  mol m -2 s -1 Pa -1 . The CO 2 flux and CO 2 /CH 4 mixture selectivity reach 3.6 Nm 3 m -2 h -1 and 43 even at feed pressure up to 31 bar. Such strategy could pave the way of all-silica zeolite membranes to practical applications., (© 2022. The Author(s).)

Water polo is a team sport that has been suffering rule changes aiming for a more attractive game. Our goal was to unveil whether different offensive playing styles or methods were adopted by elite national teams from Eastern Europe and from other world countries after the new rules framework was applied at the 2019 FINA World Championship. Additionally, we questioned whether those rules induced a more dynamic game. A total of 648 offensive sequences from games contested by the top-six ranked national squads were analysed. Descriptive statistics, parametric and nonparametric tests were computed, and the effect size was used. The eastern Europeans were the tallest (t (76) = −4.081; p < 0.001, d = 0.42) and the Hungarians were higher than Italians (p = 0.005, dz = −0.41). Offensive time length differed between teams (H (5) = 30.50, p < 0.001) with Serbia being the fastest (Mdn = 22 s). In successful attacks without extra time, Italy was quicker than Spain (17.5 vs. 25.0 s; p = 0.031, dz = −0.36) scoring 30% of their total goals under 20 s, while Australia up to 24% and Croatia, Hungary and Spain ≤ 16.0%. When power-play occurred, the teams’ pass action was different (H (5) = 15.99, p < 0.007), with Italy performing more passes than counterparts, especially Serbia (Mdn = 13 vs. 9, respectively; p= 0.003, dz = 0.20) and with the exception of Hungary. Through fast play sequences, Italy, Serbia and Australia scored up to 33% of their goals, while Spain, Croatia, and Hungary scored ≤ 15%. The power-play contributed to ≥50% of teams’ goals, except for Spain and Australia (48 and 45%, respectively). Playing styles commonly attributed to Eastern vs. non-Eastern Europeans and other worldwide national teams such as Australia were not confirmed. However, offensive trends were perceived and described for the first time, and some base guidelines were suggested to distinguish the static or positional vs. a more dynamic playing model. Rule changes did not seem to induce the expected effects on game dynamics.

Synthetic and naturally occurring forms of tricopper orthotellurate, Cu II 3 Te VI O 6 (the mineral mcalpineite) have been investigated by 3D electron diffraction (3D ED), X-ray powder diffraction (XRPD), Raman and infrared (IR) spectroscopic measurements. As a result of the diffraction analyses, Cu II 3 Te VI O 6 is shown to occur in two polytypes. The higher-symmetric Cu II 3 Te VI O 6 -1C polytype is cubic, space group Ia3, with a = 9.537 (1) Å and V = 867.4 (3) Å 3 as reported in previous studies. The 1C polytype is a well characterized structure consisting of alternating layers of Cu II O 6 octahedra and both Cu II O 6 and Te VI O 6 octahedra in a patchwork arrangement. The structure of the lower-symmetric orthorhombic Cu II 3 Te VI O 6 -2O polytype was determined for the first time in this study by 3D ED and verified by Rietveld refinement. The 2O polytype crystallizes in space group Pcca, with a = 9.745 (3) Å, b = 9.749 (2) Å, c = 9.771 (2) Å and V = 928.3 (4) Å 3 . High-precision XRPD data were also collected on Cu II 3 Te VI O 6 -2O to verify the lower-symmetric structure by performing a Rietveld refinement. The resultant structure is identical to that determined by 3D ED, with unit-cell parameters a = 9.56157 (19) Å, b = 9.55853 (11) Å, c = 9.62891 (15) Å and V = 880.03 (2) Å 3 . The lower symmetry of the 2O polytype is a consequence of a different cation ordering arrangement, which involves the movement of every second Cu II O 6 and Te VI O 6 octahedral layer by (1/4, 1/4, 0), leading to an offset of Te VI O 6 and Cu II O 6 octahedra in every second layer giving an ABAB* stacking arrangement. Syntheses of Cu II 3 Te VI O 6 showed that low-temperature (473 K) hydrothermal conditions generally produce the 2O polytype. XRPD measurements in combination with Raman spectroscopic analysis showed that most natural mcalpineite is the orthorhombic 2O polytype. Both XRPD and Raman spectroscopy measurements may be used to differentiate between the two polytypes of Cu II 3 Te VI O 6 . In Raman spectroscopy, Cu II 3 Te VI O 6 -1C has a single strong band around 730 cm -1 , whereas Cu II 3 Te VI O 6 -2O shows a broad double maximum with bands centred around 692 and 742 cm -1 .

At its core, reticular chemistry has translated the precision and expertise of organic and inorganic synthesis to the solid state. While initial excitement over metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) was undoubtedly fueled by their unprecedented porosity and surface areas, the most profound scientific innovation of the field has been the elaboration of design strategies for the synthesis of extended crystalline solids through strong directional bonds. In this contribution we highlight the different classes of reticular materials that have been developed, how these frameworks can be functionalized, and how complexity can be introduced into their backbones. Finally, we show how the structural control over these materials is being extended from the molecular scale to their crystal morphology and shape on the nanoscale, all the way to their shaping on the bulk scale., (© 2021 Wiley-VCH GmbH.)

The organic components in metal-organic frameworks (MOFs) are unique: they are embedded in a crystalline lattice, yet, as they are separated from each other by tunable free space, a large variety of dynamic behavior can emerge. These rotational dynamics of the organic linkers are especially important due to their influence over properties such as gas adsorption and kinetics of guest release. To fully exploit linker rotation, such as in the form of molecular machines, it is necessary to engineer correlated linker dynamics to achieve their cooperative functional motion. Here, we show that for MIL-53, a topology with closely spaced rotors, the phenylene functionalization allows researchers to tune the rotors' steric environment, shifting linker rotation from completely static to rapid motions at frequencies above 100 MHz. For steric interactions that start to inhibit independent rotor motion, we identify for the first time the emergence of coupled rotation modes in linker dynamics. These findings pave the way for function-specific engineering of gear-like cooperative motion in MOFs.

Shooting performance of globally ranked winning, drawing and losing water polo teams was compared, and technical and tactical success indicators were identified. In total, 886 shots from a world championship final round were videotaped and teams were clustered for a performance evaluation (considering differences between game outcomes). Shooting speeds were assessed by a radar, with higher values observed at further distances from the goal than in the central area close to the goal (p ≤ 0.00, ES: 2.54). Shots tended to be more frequent from the central corridor, with ≤50% and >75% relative shot efficacy attained from field areas 3 and 6; winning teams obtained better results. Furthermore, winners had greater success than losers when shooting from field area 2 (p ≤ 0.04, ES: 1.13) and towards the goal zone 2 (p < 0.03, ES: 1.10). They also attained better efficacy regarding shots towards goal zone 1, had better efficacy on the part of centre-forwards (p ≤ 0.05, ES: 0.85-1.27), and were more effective regarding shots without a frontal defensive block. In addition, contingency analysis highlighted shots performed from field area 6, without a defensive block, toward the bottom left goal corner, and through man-up play as success indicators (all for p ≤ 0.005). We concluded that world-level winning teams homogeneously distributed their shot opportunities at the second offensive line with balanced efficacy, creating variability and uncertainty in their opponents' defensive action. Elite level players must be capable of interpreting game situations with intelligence and proper decision making. This information may be useful for improving teams performance., (© 2020 Sofia Canossa, José Arturo Abraldes, Luísa Estriga, Ricardo J Fernandes, Júlio Garganta, published by Sciendo.)

A modulated synthesis approach based on the chelating properties of oxalic acid (H 2 C 2 O 4 ) is presented as a robust and versatile method to achieve highly crystalline Al-based metal-organic frameworks. A comparative study on this method and the already established modulation by hydrofluoric acid was conducted using MIL-53 as test system. The superior performance of oxalic acid modulation in terms of crystallinity and absence of undesired impurities is explained by assessing the coordination modes of the two modulators and the structural features of the product. The validity of our approach was confirmed for a diverse set of Al-MOFs, namely X-MIL-53 (X=OH, CH 3 O, Br, NO 2 ), CAU-10, MIL-69, and Al(OH)ndc (ndc=1,4-naphtalenedicarboxylate), highlighting the potential benefits of extending the use of this modulator to other coordination materials., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Every measurement technique operates on a given timescale and measurements using emissive small molecule sensors are no exception. A family of luminescent sensors providing first optical characterization of dynamic phenomena in polymers at a timescale of several microseconds is described. This performance originates from the dynamics manifested in the excited state of the sensor molecules where diffusioncontrolled events select the emission color while radiative phenomena define the global operation timescale. Since the mechanism responsible for signal generation is confined to the short lived excited state of emissive probe, it is possible observe an unprecedented link between the timescale of sensory action and that of photoluminescence. An application of this new methodology is demonstrated by performing general, short timescale detection of glass transitions in a temperature ranges precluding the informative range of conventional techniques by tens of degrees., (© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Objective: To report the stabilization of urinary glycosaminoglicans (GAG) excretion and clinical improvements in patients with mucopolysaccharidosis type I (MPS I) under an alternative dose regimen of laronidase of 1.2 mg/kg every other week., Methods: We participated in a dose-optimization trial for laronidase in MPS-I patients using four alternative regimens: 0.58 mg/kg every week, 1.2 mg/kg every two weeks, 1.2 mg/kg every week and 1.8 mg/kg every other week (EOW). After the trial ended, the patients resumed the recommended dose and regimen of 0.58 mg/kg every week. Under this regimen, some patients presented difficulties in venous access and were unable to commute weekly to the treatment center. Therefore, we used an alternative regimen that consisted of 1.2 mg/kg EOW in eight patients. A retrospective study of medical records of MPS-I patients who underwent both enzyme replacement therapy (ERT) regimens, of 0.58 mg/kg every week and 1.2 mg/kg EOW, was done., Results: Patients remained clinically stable under the alternative regimen, did not present elevation of urinary GAG nor any adverse event.Conclusions: The switch of dose regimen to 1.2 mg/kg EOW of laronidase was safe, and did not cause any clinical worsening in patients who had been previously under standard dose ERT.

Two unprecedented solid phases involving the 3,7-bis-(di-methyl-amino)-pheno-thia-zin-5-ium cation, i.e. methyl-ene blue ( MB + ), have been obtained and structurally characterized. In the crystals of 3,7-bis-(di-methyl-amino)-pheno-thia-zin-5-ium chloride dihydrate, C 16 H 18 N 3 S + ·Cl - ·2H 2 O ( I ) and 3,7-bis-(di-methyl-amino)-pheno-thia-zinium bis-ulfite, C 16 H 18 N 3 S + ·HSO 4 - ( II ), the cationic dye mol-ecules are planar and disposed in an anti-parallel mode, showing π-π stacking inter-actions, with mean inter-planar distances of 3.326 (4) and 3.550 (3) Å in ( I ) and ( II ), respectively. In compound ( I ), whose phase was found affected by merohedral twinning [BASF = 0.185 (3)], the presence of water mol-ecules allows a network of hydrogen bonds involving MB + as both a donor and an acceptor, whereas in compound ( II ), the homo-inter-action of the anions causes an effective absence of classical hydrogen-bond donors. This substantial difference has important consequences for the stacking geometry and supra-molecular inter-actions of the MB + cations, which are analysed by Hirshfeld fingerprint plots and subsequently discussed.

The aromatic methylene blue cation (MB + ) shows unprecedented ligand behavior in the X-ray structures of the trigonal-planar (TP) complexes MBMCl 2 (M = Cu I , Ag I ). The two isostructural compounds were exclusively synthesized by grinding together methylene blue chloride and MCl solids. Only in the case of AuCl did the technique lead to a different, yet isoformular, Au I derivative with separated MB + and AuCl 2 - counterions and no direct N-Au linkage. While the density functional theory (DFT) molecular modeling failed in reproducing the isolated Cu and Ag complexes, the solid-state program CRYSTAL satisfactorily provided for Cu the correct TP building block associated with a highly compact π stacking of the MB + ligands. In this respect, the dispersion interactions, evaluated with the DFT functional, provide to the system an extra energy, which likely supports the unprecedented metal coordination of the MB + cation. The feature seems governed by subtle chemical factors, such as, for instance, the selected metal ion of the coinage triad. Thus, the electronically consistent Au I ion does not form the analogous TP building block because of a looser supramolecular arrangement. In conclusion, while a given crystalline design is generally fixed by the nature of the building block, a peculiarly efficient supramolecular packing may stabilize an otherwise unattainable metal complex.