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By reacting a 3,6-ditriazolyl-2,5-dihydroxybenzoquinone (H 2 trz 2 An) anilato linker with Ln III ions (Ln III = Dy, Tb, Ho), two different series of polymorphs, formulated as [Ln 2 (trz 2 An) 3 (H 2 O) 4 ] n ·10H 2 O (Dy III , 1a; Tb III , 2a, Ho III , 3a) and [Ln 2 (trz 2 An) 3 (H 2 O) 4 ] n ·7H 2 O (Dy III , 1b, Tb III , 2b, Ho III , 3b) have been obtained. In these series the two Dy III -coordination networks (1a and 1b) and the Tb III -coordination polymer (2b) show a Single Ion Magnet (SIM) behavior. 1-3a MOFs show reversible structural flexibility upon removal of a coordinated water molecule from a distorted hexagonal 2D framework to a distorted 3,6-brickwall rectangular 3D structure in [Ln 2 (trz 2 An) 3 (H 2 O) 2 ] n ·2H 2 O (Dy III , 1a_des; Tb III , 2a_des, Ho III , 3a_des) involving shrinkage/expansion of the hexagonal-rectangular networks. Noteworthy, 2b represents the first example of a Tb III -anilate-based coordination polymer showing SIM behaviour to date and the best SIM properties within the polymorphs. Theoretical investigation via ab initio CASSCF calculations supports this behavior, since 2b shows less mixing between the m J states of the ground state among all the studied complexes., Competing Interests: There are no conflicts to declare., (This journal is © the Partner Organisations.)

This work challenges the conventional approach of using Nd III 4 F 3/2 lifetime changes for evaluating the experimental Nd III → Yb III energy transfer rate and efficiency. Using near-infrared (NIR) emitting Nd:Yb mixed-metal coordination polymers (CPs), synthesized via solvent-free thermal grinding, we demonstrate that the Nd III [ 2 H 11/2 → 4 I 15/2 ] → Yb III [ 2 F 7/2 → 2 F 5/2 ] pathway, previously overlooked, dominates energy transfer due to superior energy resonance and J -level selection rule compatibility. This finding upends the conventional focus on the Nd III [ 4 F 3/2 → 4 I 11/2 ] → Yb III [ 2 F 7/2 → 2 F 5/2 ] transition pathway. We characterized Nd 0.890 Yb 0.110 (BTC)(H 2 O) 6 as a promising cryogenic NIR thermometry system and employed our novel energy transfer understanding to perform simulations, yielding theoretical thermometric parameters and sensitivities for diverse Nd:Yb ratios. Strikingly, experimental thermometric data closely matched the theoretical predictions, validating our revised model. This novel perspective on Nd III → Yb III energy transfer holds general applicability for the Nd III /Yb III pair, unveiling an important spectroscopic feature with broad implications for energy transfer-driven materials design., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

By combining 3,6- N -ditriazolyl-2,5-dihydroxy-1,4-benzoquinone (H 2 trz 2 An) with NIR-emitting Er III ions, two different 3D neutral polymorphic frameworks (1a and 1b), differing in the number of uncoordinated water molecules, formulated as [Er 2 (trz 2 An) 3 (H 2 O) 4 ] n · x H 2 O ( x = 10, a; x = 7, b), have been obtained. The structure of 1a shows layers with (6,3) topology forming six-membered rings with distorted hexagonal cavities along the bc plane. These 2D layers are interconnected through the N4 atoms of the two pendant arms of the trz 2 An linkers, leading to a 3D framework, where neighboring layers are eclipsed along the a axis, with hexagonal channels filled with water molecules. In 1b, layers with (6,3) topology in the [101] plane are present, each Er III ion being connected to three other Er III ions through bis-bidentate trz 2 An linkers, forming rectangular six-membered cavities. 1a and 1b are multifunctional materials showing coexistence of NIR emission and field-induced slow relaxation of the magnetization. Remarkably, 1a is a flexible MOF, showing a reversible structural phase transition involving shrinkage/expansion from a distorted hexagonal 2D framework to a distorted 3,6-brickwall rectangular 3D structure in [Er 2 (trz 2 An) 3 (H 2 O) 2 ] n ·2H 2 O (1a_des). This transition is triggered by a dehydration/hydration process under mild conditions (vacuum/heating to 360 K). The partially dehydrated compound shows a sizeable change in the emission properties and an improvement of the magnetic blocking temperature with respect to the hydrated compound, mainly related to the loss of one water coordination molecule. Theoretical calculations support the experimental findings, indicating that the slight improvement observed in the magnetic properties has its origin in the change of the ligand field around the Er III ion due to the loss of a water molecule., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The synthesis, structural and photophysical characterization, and theoretical studies on homo/heteroleptic neutral 2D-layered coordination polymers (CPs), obtained by combining the Er III ion with chlorocyananilate (ClCNAn) and/or tetrafluoroterephthalate (F 4 BDC) linkers, are herein reported. The structure of the heteroleptic Er III -based CP, formulated as [Er 2 (ClCNAn) 2 (F 4 BDC)(DMSO) 6 ] n ( 1 ) is also reported. 1 crystallizes in the triclinic P 1̅ space group, and the structure consists of neutral 2D layers formed by Er III ions linked through the two linkers oriented in such a way that the neighboring 2D layers are eclipsed along the a axis, leading to parallelogram-like cavities. Photophysical measurements highlight the prominent role of chlorocyananilate linkers as optical antennas toward lanthanide ions, while wave-function-theory analysis supports the experimental findings, providing evidence for the effect of ligand substitution on the luminescence properties of homo/heteroleptic 2D CPs.

Achieving metal-organic frameworks (MOFs) in the form of nanoparticles (NanoMOFs) represents a recent challenge due to the possibility to combine the intrinsic porosity of these materials with the nanometric dimension, a fundamental requirement for strategic biomedical applications. In this outlook we envision the current/future opportunities of the NanoMOFs in the field of biomedicine, with particular emphasis on (i) biocompatible MOFs composition; (ii) MOFs miniaturization and (iii) nanoMOFs applications.

The potential of silicon-based fluorescent platforms for the detection of trace toxic metal ions was investigated in an aqueous environment. To this aim, silicon chips were first functionalized with amino groups, and fluorescein organic dyes, used as sensing molecules, were then covalently linked to the surface via formation of thiourea groups. The obtained hybrid heterostructures exhibited high sensitivity and selectivity towards copper(ii), a limit of detection compatible with the recommended upper limits for copper in drinking water, and good reversibility using a standard metal-chelating agent. The fluorophore-analyte interaction mechanism at the basis of the reported fluorescence quenching, as well as the potential of performance improvement, were also studied. The herein presented sensing architecture allows, in principle, tailoring of the selectivity towards other metal ions by proper fluorophore selection, and provides a favorable outlook for integration of fluorescent chemosensors with silicon photonics technology., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Electrocrystallization of the bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) organic donor in the presence of the [Fe(ClCNAn) 3 ] 3- tris(chlorocyananilato)ferrate(III) paramagnetic anion in different stoichiometric ratios and solvent mixtures afforded two different hybrid systems formulated as [BEDT-TTF] 4 [Fe(ClCNAn) 3 ]·3H 2 O ( 1 ) and [BEDT-TTF] 5 [Fe(ClCNAn) 3 ] 2 ·2CH 3 CN ( 2 ) (An = anilato). Compounds 1 and 2 present unusual structures without the typical segregated organic and inorganic layers, where layers of 1 are formed by Λ and Δ enantiomers of the anionic paramagnetic complex together with mixed-valence BEDT-TTF tetramers, while layers of 2 are formed by Λ and Δ enantiomers of the paramagnetic complex together with dicationic BEDT-TTF dimers and monomers. Compounds 1 and 2 show semiconducting behaviors with room-temperature conductivities of ca. 6 × 10 -3 S cm -1 (ambient pressure) and 1 × 10 -3 S cm -1 (under applied pressure of 12.1 GPa), respectively, due to strong dimerization between the donors. Magnetic measurements performed on compound 1 indicate weak antiferromagnetic coupling between high-spin Fe III ( S Fe = 5/2) and mixed-valence radical cation diyads (BEDT-TTF) 2 + ( S rad = 1/2) mediated by the anilate ligands, together with an important Pauli paramagnetism typical for conducting systems.

A series of two-dimensional (2D)-layered coordination polymers (CPs) based on the heterosubstituted anilate ligand ClCNAn 2- derived from 3-chloro-6-cyano-2,5-dihydroxybenzoquinone and Dy III are reported. By changes in the synthetic methods (layering technique, solvothermal or conventional one-pot reactions) and conditions (solvent, concentration, etc.), different types of 2D extended networks could be prepared and structurally characterized. Compounds 1 and 1' , two polymorphs with the formula [Dy 2 (ClCNAn) 3 (DMSO) 6 ] n ·(H 2 O) x [ x = 7 ( 1 ), 0 ( 1' )], were prepared by a conventional one-pot reaction and recrystallized at different concentrations. Compound 2 , formulated as [Dy 2 (ClCNAn) 3 (DMF) 6 ] n , was prepared by a layering technique, while compound 3 , formulated as {(Me 2 NH 2 ) 2 [Dy 2 (ClCNAn) 4 (H 2 O) 2 ]·(DMF) 2 ·(H 2 O) 5 } n , was obtained by a solvothermal method. Compounds 1 and 2 are neutral 2D CPs of the ClCNAn 2- ligand and Dy III ions, while 3 presents 2D anionic layers of [Dy 2 (ClCNAn) 4 (H 2 O) 2 ] 2- alternating with cationic layers of Me 2 NH 2 + ions. These compounds show very diverse networks, with compound 1 forming 2D (8,3) and (4,3) topology with eight- and four-membered rings with square cavities, 1' and 2 , respectively, a 2D (6,3) topology with six-membered rings (a rectangular cavity for 1' and a regular hexagonal cavity for 2 ), and 3 a 2D (4,4) topology with distorted square cavities. In this respect, 1 and 1' represent the first examples of polymorphism in the family of anilate-based CPs. Thermal analysis measurements (differential scanning calorimetry and thermogravimetry) show an exothermic polymorphic transformation from the kinetically stable 1' phase to the thermodynamically stable phase 1 . The magnetic behavior of 1 - 3 very likely indicates depopulation of the m J levels, while the presence of weak antiferromagnetic coupling between the Dy III centers mediated by the anilate bridge cannot be excluded.

A Raman study on Zinc-substituted Cobalt ferrites, with different Zn(II) contents in each sample of formula: CoFe₂O₄ ( 1 ), Zn 0.30 Co 0.70 Fe 2.00 O₄ ( 2 ), Zn 0.46 Co 0.54 Fe 2.02 O₄ ( 3 ), Zn 0.53 Co 0.47 Fe 2.02 O₄ ( 4 ) is reported. These samples show the same crystallite size (∼6 nm), particle size (∼7 nm) and particle size distribution (∼20%) and they have been synthesized through heating up surfactant-assisted thermal decomposition of metalorganic precursors. The effect of Zn(II) substitution in the cationic distribution is investigated by using the known metal-oxygen vibrational modes in tetrahedral and octahedral sites. The presence of Zn(II) metal ion is determined through the band at 150 cm -1 (T 2g (1) phonon mode), which is not present in the pure Co-ferrite, a blue-shift of the E g vibrational mode depending on Zn(II)/Co(II) cationic distribution and a shoulder at ∼250 cm -1 , which appears when zinc enters in the structure, and a broadening and a red-shift in the A 1g phonon mode is observed in Raman spectra of 2-4 samples. Interestingly the latter represents a potential key probe to monitor the Zn(II) presence in Zn-substituted Co-ferrites.

The mixed-valence Fe II Fe III 2D coordination polymer formulated as [TAG][Fe II Fe III (ClCNAn) 3 ]·(solvate) 1 (TAG = tris(amino)-guanidinium, ClCNAn 2- = chlorocyanoanilate dianionic ligand) crystallized in the polar trigonal space group P3. In the solid-state structure, determined both at 150 and at 10 K, anionic 2D honeycomb layers [Fe II Fe III (ClCNAn) 3 ] - establish in the ab plane, with an intralayer metal-metal distance of 7.860 Å, alternating with cationic layers of TAG. The similar Fe-O distances suggest electron delocalization and an average oxidation state of +2.5 for each Fe center. The cation imposes its C 3 symmetry to the structure and engages in intermolecular N-H···Cl hydrogen bonding with the ligand. Magnetic susceptibility characterization indicates magnetic ordering below 4 K and the presence of a hysteresis loop at 2 K with a coercive field of 60 Oe. Mössbauer measurements are in agreement with the existence of Fe(+2.5) ions at RT and statistic charge localization at 10 K. The compound shows semiconducting behavior with the in-plane conductivity of 2 × 10 -3 S/cm, 3 orders of magnitude higher than the perpendicular one. A small-polaron hopping model has been applied to a series of oxalate-type Fe II Fe III 2D coordination polymers, providing a clear explanation on the much higher conductivity of the anilate-based systems than the oxalate ones.

Radical cation salts composed of a bis(ethylenedithio)tetrathiafulvalene (ET) donor with homo-/heterosubstituted Cl/CN anilic acids as purely organic molecular conducting materials formulated as [BEDT-TTF] 2 [HClCNAn] (1) and [BEDT-TTF][HCl 2 An] (2) have been prepared by electrocrystallization. Compounds 1 and 2 crystallized in the monoclinic space group P2/c for 1 and I2/a for 2, showing segregated donor-anion layers arranged in a α'-type donor packing pattern (1) and twisted parallel columns (2), respectively. Single-crystal conductivity measurements show that 1 is a semiconductor with room-temperature conductivity of 10 -2 S cm -1 and an activation energy E a of 1900 K.

Unlabelled: Bilateral prophylactic mastectomy without reconstruction is not accepted by the majority of patients. Successful reconstruction is therefore a mandatory condition for prophylactic mastectomy. Of the many options for autologous breast reconstruction, the deep inferior epigastric perforator (DIEP) flap best meets requirements for bilateral reconstruction in selected patients. The goal of this study is to verify the feasibility of the procedure in our conditions and to find out how it is accepted by patients. We present 55 consecutive patients who were scheduled for bilateral DIEP flap reconstruction during a 4-year period. We reviewed medical charts, performed clinical assessments and processed anonymous questionnaires. There were 77 immediate and 33 delayed breast reconstructions. There was 100% flap survival and no microanastomoses revisions. In 11 patients (10%) the surgeon preferred to convert the DIEP into a mini transverse rectus abdominis muscle (miniTRAM) flap in order to provide adequate blood supply., Complications: revision for haematoma under the flap in four patients (7.2%), excessive blood loss in four patients (7.2%) and partial mastectomy skin flap necrosis in 10 immediate breast reconstructions (12.9%). Patients' evaluation of the aesthetic result was good or excellent in 96.2% of cases. In 33.9% of patients the postoperative quality of life was considered unchanged and 50.9% of them it even improved. The DIEP flap is recommended for bilateral breast reconstruction. Occasional conversion into a miniTRAM flap can increase the total flap survival rate. Bilateral prophylactic mastectomy and DIEP flap reconstruction are very well accepted by patients.

Background: Unilateral breast reconstruction with a free abdominal TRAM or DIEP flap restores the shape of the amputated breast with acceptable donor site morbidity. In patients with small breasts and ample lower abdominal tissue this can be achieved by using only a hemi-abdominal flap. In these cases, the contra-lateral flap is usually discarded, but it could potentially be left in situ as a "spare" hemi-abdominal flap, especially in patients at high risk for contra-lateral breast cancer or flap failure. We report our early experience with this preservation technique., Material and Methods: The authors report two cases of unilateral breast reconstruction with hemi-abdominal DIEP free flaps in women at high risk for contra-lateral breast cancer and/or flap failure, who opted not to have prophylactic contra-lateral mastectomies. They consented to having the unused "spare" hemi-abdominal deepithelialized flap left in situ in case the need for a secondary flap arose., Results: The "spare" hemi-abdominal flap was used for immediate reconstruction as an SIEA free flap when the first patient's original flap necrosed secondary to microcirculation problems. The second patient's spare flap was left in situ by burying it after de-epithelialization., Conclusions: We believe that patients undergoing unilateral breast reconstruction who are at high risk for contra-lateral breast cancer and/or free flap failure, and who choose not to undergo an immediate contra-lateral prophylactic mastectomy, should have the "spare" hemi-abdominal flap buried. This tissue could be used as a potential bailout flap in cases of original flap failure or for contralateral breast reconstruction at a later date.

From December 2001 to September 2005, the technique of total penile reconstruction with a reinnervated free latissimus dorsi myocutaneous flap was used in 22 patients (24-38 years old) with gender dysphoria. These patients were followed up for at least 11 months (range, 11-44 months). All flaps survived. Complications include hematoma (7 cases), vascular thrombosis (2 cases), partial necrosis (1 case), excessive swelling of the neophallus (3 cases), and skin graft loss at the donor site (1 case). Of the 19 patients included in the final evaluation, the transplanted muscle was able to obtain contraction in 18 (95%) cases and 8 patients (42%) had sexual intercourse by contracting the muscle to stiffen and move the neopenis. The described technique of neophalloplasty proved to be a reliable technique and the muscle movement in the neophallus can be expected in almost all cases. The muscle contraction in the neophallus leads to "paradox" erection-stiffening, widening, and shortening of the neopenis, which allows for sexual intercourse in some patients. Subsequent reconstruction of the urethra is possible.

Twenty two patients with gender dysphoria underwent neo-phalloplasties using a novel technique. Latissimus dorsi musculocutaneus re-innervated free flap was used to allow voluntary rigidity of the neo-penis. From the first 22 patients, 18 have obtained motoric function of reconstructed penis; the "paradox erection" was obtained. 14 patients came for examination after a follow-up period of mean 26.4 months. We evaluated the motility and shape changes of neo-phallus measuring its different size and dimension during relax and muscle contraction. The range of neo-phallus length in relaxed position was between 7 and 17 cm (mean 12.2 cm), its circumference in the same position had a range between 13 and 20 cm (mean 13.7 cm). All patients were able to contract the muscle with an average length reduction of 3.08 cm and an average circumference enlargement of 4 cm. In this study, the dimensions and motility were quantified demonstrating the neo-phallus function and size changes during sexual intercourse.

We report a case of a 17-year-old patient who sustained multiple finger contusions on the left hand. After thorough debridement, the volar and dorsal defects of the middle finger were covered simultaneously with bilobed arterialized venous free flap from the left forearm. The flap was composed of 2 paddles, which were connected by a subcutaneous bridge containing a subcutaneous venous network. The subdermal plexus in the bridge was interrupted with no impairment of blood supply to the second cutaneous paddle. The flap survived completely with only temporary mild venous congestion. Excellent functional and cosmetic result was reached. We consider bilobed arterialized venous free flap as a useful option for coverage of concomitant volar and dorsal digital defects.