Mechanochemically-induced glass formation from two-dimensional hybrid organic-inorganic perovskites.

Hybrid organic-inorganic perovskites (HOIPs) occupy a prominent position in the field of materials chemistry due to their attractive optoelectronic properties. While extensive work has been done on the crystalline materials over the past decades, the newly reported glasses formed from HOIPs open up a new avenue for perovskite research with their unique structures and functionalities. Melt-quenching is the predominant route to glass formation; however, the absence of a stable liquid state prior to thermal decomposition precludes this method for most HOIPs. In this work, we describe the first mechanochemically-induced crystal-glass transformation of HOIPs as a rapid, green and efficient approach for producing glasses. The amorphous phase was formed from the crystalline phase within 10 minutes of ball-milling, and exhibited glass transition behaviour as evidenced by thermal analysis techniques. Time-resolved in situ ball-milling with synchrotron powder diffraction was employed to study the microstructural evolution of amorphisation, which showed that the crystallite size reaches a comminution limit before the amorphisation process is complete, indicating that energy may be further accumulated as crystal defects. Total scattering experiments revealed the limited short-range order of amorphous HOIPs, and their optical properties were studied by ultraviolet-visible (UV-vis) spectroscopy and photoluminescence (PL) spectroscopy.

Bone Tissue Engineering Scaffolds: Materials and Methods.

The wide development in biomedical, regenerative medicine, and surgical techniques has ensured that new technologies are developed to improve patient-specific treatment and care. Tissue engineering is a special field in biomedical engineering that works toward cell development using scaffolds. Bone tissue engineering is a separate branch of tissue engineering, in which the construction of bone, functionalities of bone, and bone tissue regeneration are studied in detail to repair or regenerate new functional bone tissues. In India alone, people suffering from bone diseases are extensive in numbers. Almost 15% to 20% of the population suffers from osteoporosis. Bone scaffolds are proving to be an excellent solution for osseous abnormalities or defect treatment. Scaffolds are three dimensional (3D) and mostly porous structures created to enhance new tissue growth. Bone scaffolds are specially designed to promote osteoinductive cell growth, expansion, and migration on their surface. This review article aims to provide an overview of possible bone scaffolding materials in practice, different 3D techniques to fabricate these scaffolds, and effective bone scaffold characteristics targeted by researchers to fabricate tissue-engineered bone scaffolds.

Coastal groundwater quality prediction using objective-weighted WQI and machine learning approach.

The water quality index (WQI) is a globally accepted guideline to indicate the water quality standard of any groundwater resource. Water levels in existing groundwater sources are declining in several coastal zones. Therefore, for monitoring water quality and improving water management, the prediction and identification of groundwater status by an effective technique with higher accuracy is urgently needed. Therefore, this research aims to find an effective model for WQI prediction by comparing entropy and critic weight-based WQI (ENW-WQI and CRITIC-WQI) with multi-layer perceptron artificial neural network (MLP-ANN) technique and also to identify contaminated zones using GIS. Initially, 1000 water sampling datasets with concentrations of several water quality parameters of different coastal blocks of eastern India during 2018 to 2022 are considered for the estimation of ENW-WQI and CRITIC-WQI. It shows 65% and 67% of the samples are excellent to good for drinking. ENW-WQI and CRITIC-WQI-based MLP-ANN models have been established considering different data portioning and hidden neuron numbers. Input variables and appropriate dataset partitioning with hidden neurons for models obtained from correlation and trial-error analysis. Spatial distribution maps are also produced for calculated WQIs using inverse distance weighted interpolation approaches. Three fitting models are obtained: ENW-WQI-MLP-ANN, CRITIC-WQI-MLP-ANN-I and CRITIC-WQI-MLP-ANN-II. CRITIC-WQI-MLP-ANN-II model (data ratio 85:15, network structure 6-12-1, R2 = 0.986, NSE = 0.98, and error rate 0.49%) provides the best accuracy in WQI prediction. The GIS-based WQI maps record several areas related to drinking water quality. The results of this research can help in planning the provision of safe drinking water in the future.

Sarcopenia and Osteoporosis.

Osteoporosis and sarcopenia are major health issues which are going to have a significant impact in an aging global population. Osteoporosis, which reduces bone density and increases fracture risk, and sarcopenia, which causes muscle loss and strength loss, have a complicated risk profile with consequences that go beyond bone and muscle health. This chapter illuminates the complex link between osteoporosis and sarcopenia, including overlapping causes, clinical consequences, and new treatments. This chapter covers bone and muscle biology, age-related changes that cause osteoporosis and sarcopenia, and the importance of physical exercise and diet in their prevention and management. It also discusses clinical evaluation methods, risk assessment and diagnostic criteria for early diagnosis and intervention. Novel therapies and continuing research in the management of osteoporosis and sarcopenia are also discussed. Medications, exercise, and nutrition can promote bone and muscle health. This chapter aims to explore the recent concepts by elucidating the complex relationship between osteoporosis and sarcopenia and advocating for integrated care paradigms.

Creating glassy states of dicarboxylate-bridged coordination polymers.

We report the direct formation of dicarboxylate-based coordination polymer glasses through thermal dehydration. The rearrangement of the coordination networks caused by dehydration was monitored by in situ powder X-ray diffraction, infrared spectroscopy, and synchrotron X-ray characterizations. The microporosity and mechanical properties of these glasses were investigated.

MLR index-based principal component analysis to investigate and monitor probable sources of groundwater pollution and quality in coastal areas: a case study in East India.

Identifying groundwater contamination sources and supervising groundwater quality conditions are urgently needed to protect the groundwater resources of coastal areas like Contai of India, as communities here are heavily relying on groundwater which deteriorates progressively. So current research aims to address in detail about origins and influencing factors of groundwater contamination, status, and monitoring water quality by employing extremely useful leading technologies like principal component and factor analyses (PCA/FA), groundwater quality index (GWQI), and multiple linear regression (MLR) that helps to simplify complicated works instead of the conventional methods. Eight groundwater quality parameters were evaluated here, such as pH, TH (total hardness), Tur (turbidity), EC (electrical conductivity), TDS (total dissolved solids), Mn (manganese), Fe (iron), and Cl (chloride) for 38 sites. Three principal components with ~ 81% of the total variance were extracted from the PCA/FA analysis. The origin of maximum loadings of each factor is identified as a result of saline water, disintegration and leaching process, organic or else biogenic activities, and lithogenic or otherwise non-lithogenic links through percolating water. GWQI results show that ~ 87% of the samples fall into the good category and ~ 13% of the samples fall into the poor to very poor category. A model consisting of Tur, Fe, EC, Mn, TH, and Cl as independent parameters is more feasible and is proposed to predict GWQI obtained from MLR analysis. This MLR model also suggests that turbidity with the highest beta coefficient (0.820) is a key contributor relative to the entire groundwater class in this affected area. The findings relating to this research may support the designer and officials in monitoring and protecting coastal groundwater resources like selected areas.

Breathing porous liquids based on responsive metal-organic framework particles.

Responsive metal-organic frameworks (MOFs) that display sigmoidal gas sorption isotherms triggered by discrete gas pressure-induced structural transformations are highly promising materials for energy related applications. However, their lack of transportability via continuous flow hinders their application in systems and designs that rely on liquid agents. We herein present examples of responsive liquid systems which exhibit a breathing behaviour and show step-shaped gas sorption isotherms, akin to the distinct oxygen saturation curve of haemoglobin in blood. Dispersions of flexible MOF nanocrystals in a size-excluded silicone oil form stable porous liquids exhibiting gated uptake for CO2, propane and propylene, as characterized by sigmoidal gas sorption isotherms with distinct transition steps. In situ X-ray diffraction studies show that the sigmoidal gas sorption curve is caused by a narrow pore to large pore phase transformation of the flexible MOF nanocrystals, which respond to gas pressure despite being dispersed in silicone oil. Given the established flexible nature and tunability of a range of MOFs, these results herald the advent of breathing porous liquids whose sorption properties can be tuned rationally for a variety of technological applications.

Crystallization Kinetics of a Liquid-Forming 2D Coordination Polymer.

We investigated a mechanism of crystal melting and crystallization behavior of a two-dimensional coordination polymer [Ag2(L1)(CF3SO3)2] (1, L1 = 4,4'-biphenyldicarbonitrile) upon heating-cooling processes. The crystal showed melting at 282 °C, and the following gentle cooling induced the abrupt crystallization at 242 °C confirmed by DSC. A temperature-dependent structural change has been discussed through calorimetric, spectroscopic, and mechanical measurements. They indicated that the coordination-bond networks are partially retained in the melt state, but the melt showed a significantly low viscosity of 9.8 × 10-2 Pa·s at Tm which is six orders lower than that of ZIF-62 at Tm (435 °C). Rheological studies provided an understanding of the fast relaxation dynamics for the recrystallization process, along with that the high Tm provides enough thermal energy to crossover the activation energy barrier for the nucleation. The isothermal crystallization kinetics through calorimetric measurements with applying the Avrami equation identified the nature of the nuclei and its crystal growth mechanism.

Photoluminescent coordination polymer bulk glasses and laser-induced crystallization.

We synthesized luminescent coordination polymer glasses composed of d10 metal cyanides and triphenylphosphine through melt-quenching and mechanical milling protocols. Synchrotron X-ray total scattering measurements and solid-state NMR revealed their one-dimensional chain structures and high structural dynamics. Thermodynamic and photoluminescence properties were tunable by the combination of heterometallic ions (Ag+, Au+, and Cu+) in the structures. The glasses are moldable and thermally stable, and over centimeter-sized glass monoliths were fabricated by the hot-press technique. They showed high transparency over 80% from the visible to near-infrared region and strong green emission at room temperature. Furthermore, the glass-to-crystal transformation was demonstrated by laser irradiation through the photothermal effect of the glasses.

Cyclic Solid-State Multiple Phase Changes with Tuned Photoemission in a Gold Thiolate Coordination Polymer.

The discovery of a universal memory that exhibits fast access speed, high-density storage, and non-volatility has fuelled research into phase-change materials over the past decades. In spite of the efficiency of the inorganic chalcogenides for phase-change random access memory (PCRAM), they still have some inherent drawbacks, such as high temperature required for phase change and difficulty to control the domain size of the phase change, because of their brittleness. Here we present a AuI -thiolate coordination polymer which undergoes two successive phase changes on application of mild heating (<200 °C) from amorphous-to-crystalline1-to-crystalline2 phases. These transitions are reversible upon soft hand grinding. More importantly, each phase exhibits different photoluminescent properties for an efficient optical read-out. We believe that the ability of the AuI -thiolate coordination polymer to have reversible phase changes under soft conditions and at the same time to display distinct optical signals, can pave the way for the next generation of PCRAM.

Optical microscopy imaging of the thermally-induced spin transition and isothermal multi-stepped relaxation in a low-spin stabilized spin-crossover material.

The thermal spin transition and the photo-induced high-spin → low-spin relaxation of the prototypical [Fe(ptz)6](BF4)2 spin-crossover compound (ptz = 1-propyltetrazole) diluted in the isostructural ruthenium host lattice [Ru(ptz)6](BF4)2, which stabilizes the Fe(II) low-spin state, have been investigated. We demonstrate the presence of a crystallographic phase transition around 145 K (i.e. from the high-temperature ordered high-spin phase to a low-temperature disordered low-spin phase) upon slow cooling from room temperature. This crystallographic phase transition is decoupled from the thermal spin transition. A supercooled ordered low-spin phase is observed as in the pure Fe(II) analogue upon fast cooling. A similar order-disorder phase transition is also observed for pure [Ru(ptz)6](BF4)2 but at relatively higher temperature (i.e. at around 150 K) without involving any spin transition. For Ru-diluted [Fe(ptz)6]2+, the crystallographic phase transition as well as strong cooperative effects involving various degrees of elastic frustration are at the origin of stepped sigmoidal high-spin → low-spin relaxation curves, which are modelled in the framework of a classical mean field model, considering both the tunnelling and thermally activated regimes. Optical microscopy studies performed on two different single crystals showed the existence of hysteretic thermal transitions with slight domain formation, hardly visible in the static crystal images. This behavior is attributed to the double effect upon Ru dilution, which decreases the cooperative character of the transition and simultaneously reduces the optical contrast between the LS and HS states. Moreover, the transition temperature revealed to be slightly crystal dependent, highlighting the crucial role of the spatial distribution of Ru from one crystal to another, in addition to the well-known effects of crystal shape and size.

Crystal melting and vitrification behaviors of a three-dimensional nitrile-based metal-organic framework.

A three-dimensional (3D) metal-organic framework [Ag(pL2)(CF3SO3)]·2C6H6 (pL2 = 1,3,5-tris(4-cyanophenylethynyl)benzene), composed of Ag+ and tripodal nitrile ligands, was prepared to enable the investigation of its crystal melting and vitrification behaviors. The guest-free state showed a crystal melting at 271 °C, and the liquid state transformed into a glassy state via cooling. The vitrification of the crystalline compound into an amorphous glassy state was also obtained by mechanical hand-grinding. The structure of the glassy state retained the 3D networked structure, confirmed by FT-IR, X-ray absorption, and scattering measurements. The mechanically induced glass showed a small uptake of CO2 and a strong affinity for benzene and H2O vapors, confirmed by gas sorption isotherms. Powder X-ray diffraction studies have revealed that the vitrified structure returned to the original 3D crystalline structure by exposure to these vapors.

Magnetization relaxation dynamics of a rare coordinatively unsaturated Co(II) complex: experimental and theoretical insights.

A robust and unusual three coordinate Co(ii) complex [Li(DME)3][Co(L)3] (1, where L = Lithium (2,6-diisopropylphenyl) amide and DME = Dimethoxyethane) shows easy plane magnetic anisotropy (D) which is validated by variable temperature X-band EPR studies. 1 also registered with the largest anisotropic barrier (51.1 K, τ0 = 1.98 × 10-8 s; Hdc ≠ 0) to the magnetization reversal among the three coordinate Co(ii) complexes. The role of its geometry on the SH parameters and the experimental observations are rationalized by theoretical calculations including the origin of magnetic anisotropy.

Stable melt formation of 2D nitrile-based coordination polymer and hierarchical crystal-glass structuring.

Crystal melting and vitrification of nitrile-based two-dimensional coordination polymer (CP) were studied. The crystal melts at 169 °C and has a wide liquid-state temperature window of over 110 °C. The crystalline state transformed to a glassy state by melt-quench or mechanical milling. The mechanically induced glass showed permanent porosity, and it also showed glass-to-crystal transformation upon solvent treatment. Surface crystallization on top of the grain-boundary-free glass monolith was demonstrated.

Glass-phase coordination polymer displaying proton conductivity and guest-accessible porosity.

We describe the preparation of the crystalline and glassy state of a coordination polymer displaying proton conduction and guest-accessible porosity. EXAFS and solid-state NMR analyses indicated that pyrophosphate and phosphate ions are the main proton transporters in the glass and that homogeneously distributed 5-chloro-1H-benzimidazole in the glass provides the porosity.

Stabilizing Terminal Ni(III)-Hydroxide Complex Using NNN-Pincer Ligands: Synthesis and Characterization.

The reaction of [Ni(COD)2] (COD; cyclooctadiene) in THF with the NNN-pincer ligand bis(imino)pyridyl (L1) reveals a susceptibility to oxidation in an inert atmosphere ([O2] level <0.5 ppm), resulting in a transient Ni:dioxygen adduct. This reactive intermediate abstracts a hydrogen atom from THF and stabilizes an uncommon Ni(III) complex. The complex is crystallographically characterized by a molecular formula of [NiIII(L1··)2-(OH)] (1). Various isotopically labeled experiments (16O/18O) assertively endorse the origin of terminal oxygen based ligand in 1 due to the activation of molecular dioxygen. The presence of proton bound to the terminal oxygen in 1 is well supported by NMR, IR spectroscopy, DFT calculations, and hydrogen atom transfer (HAT) reactions promoted by 1. The observation of shakeup satellite peaks for the primary photoelectron lines of Ni(2p) in the X-ray photoelectron spectroscopy (XPS) unambiguously confirms the paramagnetic signature associated with the distorted square planar nickel ion, which is consistent with the trivalent oxidation state assigned for the nickel ion in 1. The variable temperature magnetic susceptibility data of 1 shows dominant antiferromagnetic interactions exist among the paramagnetic centers, resulting in an overall S = 1/2 ground state. Variable temperature X-band EPR studies performed on 1 show evidence for the S = 1/2 ground state, which is consistent with magnetic data. The unusual g-tensor extracted for the ground state S = 1/2 is analyzed under a strong exchange limit of spin-coupled centers. The electronic structure predicted for 1 is in good agreement with theoretical calculations.

Unusual Methylenediolate Bridged Hexanuclear Ruthenium(III) Complexes: Syntheses and Their Application.

Three structurally analogous hexanuclear ruthenium(III) complexes were isolated with the general molecular formula of [Ru6III(O)2(µ4-η2-η2-CH2O2)( t-BuCO2)12(L)2] where L = pyridine (1) or 4-dimethylamino pyridine (DMAP; 2) or 4-cyanopyridine (3). Complexes 1 and 3 were solved in the tetragonal I4̅c2 and P41212 space group, respectively, while 2 crystallized in the monoclinic system with P21 /c space group. In all three complexes, two oxo-centered Ru(III) triangles were bridged by a unique and a rare methylenediolate (CH2O2)2-) ligand. This (CH2O2)2- group is reported to be an intermediate, which is not isolated in its metal-free form, to date, as it is unstable. Control experiments performed evidently reveal that the unique reaction condition followed is mandatory to isolate 1-3 and the origin of (CH2O2)2- is unknown at the moment, as no precursor was used to form this intermediate. The presence of (CH2O2)2- identified through X-ray diffraction was further unambiguously confirmed by various 1D (1H and 13C) and 2D-NMR (HSQC, TOCSY, NOESY, and DEPT) spectroscopies. Direct current (dc) magnetic susceptibility measurements performed on 1 and 2 reveal the predominant antiferromagnetic exchange interaction between the Ru(III) centers result in a diamagnetic ground state at 2.0 K. The paramagnetic influence of 1-3 at room temperature evidently felt by the 1H nuclei of the (CH2O2)2- unit predominates compared to other NMR active nuclei in the complexes. The presence of an electron donating or withdrawing substituent on the terminal pyridine results in significant change in the dihedral angle of two oxo-centered triangular (Ru3O-) planes. The change in the structural parameters of 1-3 due to the substituents markedly reflected on the absorption profile and redox behavior, which are systematically investigated. Preliminary galvanostatic charge/discharge cycling experiments performed on a representative complex (3) suggest that 3 can be a promising candidate to employ as an effective multiple electron charge carrier in a nonaqueous redox flow battery.

Influence of Radicals on Magnetization Relaxation Dynamics of Pseudo-Octahedral Lanthanide Iminopyridyl Complexes.

Controlling quantum tunneling of magnetization (QTM) is a persistent challenge in lanthanide-based single-molecule magnets. As the exchange interaction is one of the key factors in controlling the QTM, we targeted lanthanide complexes with an increased number of radicals around the lanthanide ion. On the basis of our targeted approach, a family of pseudo-octahedral lanthanide/transition-metal complexes were isolated with the general molecular formula of [M(L•-)3] (M = Gd (1), Dy (2), Er (3), Y (4)) using the redox-active iminopyridyl (L•-) ligand exclusively, which possess the highest ratio of radicals to lanthanide reported for discrete metal complexes. Direct current magnetic susceptibility studies suggest that dominant antiferromagnetic interactions exist between the radical and lanthanide ions in all of the complexes, which is strongly corroborated by magnetic data fitting using a Heisenberg-Dirac-Van Vleck (HDVV) Hamiltonian (-2 J Hamiltonian). A good agreement between the fit and the experimental magnetic data obtained using g = 2, Jrad-rad = -111.9 cm-1 for 4 and g = 1.99, Jrad-rad = -111.9 cm-1, JGd-rad = -1.85 cm-1 for 1. Complex 2 shows frequency-dependent slow magnetization relaxation dynamics in the absence of an external magnetic field, while 3 shows field-induced frequency-dependent χM'' signals. An ideal octahedral geometry around the lanthanide ion is predicted to be unsuitable for the design of a single-molecule magnet (SMM); nevertheless, complex 2 exhibits slow relaxation of magnetization with a record high anisotropy barrier for a six-coordinate Dy(III) complex. A rationale for this unusual behavior is detailed and reveals the strength of the synthetic methodology developed.