Quasi-open Cu(I) sites for efficient CO separation with high O2/H2O tolerance.

Carbon monoxide (CO) separation relies on chemical adsorption but suffers from the difficulty of desorption and instability of open metal sites against O2, H2O and so on. Here we demonstrate quasi-open metal sites with hidden or shielded coordination sites as a promising solution. Possessing the trigonal coordination geometry (sp2), Cu(I) ions in porous frameworks show weak physical adsorption for non-target guests. Rational regulation of framework flexibility enables geometry transformation to tetrahedral geometry (sp3), generating a fourth coordination site for the chemical adsorption of CO. Quantitative breakthrough experiments at ambient conditions show CO uptakes up to 4.1 mmol g-1 and CO selectivity up to 347 against CO2, CH4, O2, N2 and H2. The adsorbents can be completely regenerated at 333-373 K to recover CO with a purity of >99.99%, and the separation performances are stable in high-concentration O2 and H2O. Although CO leakage concentration generally follows the structural transition pressure, large amounts (>3 mmol g-1) of ultrahigh-purity (99.9999999%, 9N; CO concentration < 1 part per billion) gases can be produced in a single adsorption process, demonstrating the usefulness of this approach for separation applications.

Isomeric Porous Cu(I) Triazolate Frameworks Showing Periodic and Aperiodic Flexibility for Efficient CO Separation.

Guest-induced (crystal-to-crystal) transformation, i.e., periodic flexibility, is a typical feature of molecule-based crystalline porous materials, but its role for adsorptive separation is controversial. On the other hand, aperiodic flexibility is rarely studied. This work reports a pair of isomeric Cu(I) triazolate frameworks, namely, α-[Cu(fetz)] (MAF-2Fa) and ß-[Cu(fetz)] (MAF-2Fb), which show typical periodic and aperiodic flexibility for CO chemical adsorption, respectively. Quantitative mixture breakthrough experiments show that, while MAF-2Fa exhibits high adsorption capacity at high pressures but negligible adsorption below the threshold pressure and with leakage concentrations of 3-8%, MAF-2Fb exhibits relatively low adsorption capacity at high pressures but no leakage (residual CO concentration <1 ppb). Tandem connection of MAF-2Fa and MAF-2Fb can combine their advantages of high CO adsorption capacities at high and low pressures, respectively. MAF-2Fa and MAF-2Fb can both keep the separation performances unchanged at high relative humidities, but only MAF-2Fb shows a unique coadsorption behavior at a relative humidity of 82%, which can be used to improve purification performances.

Above-Room-Temperature Ferroelastic Phase Transitions in Two Tetrafluoroborate-Based Hexagonal Molecular Perovskites.

ABX3-type molecular perovskites provide an important platform to tune phase transitions, via judiciously choosing A-, B-, and X-site components, to approach advanced functional materials for applications. Although tetrafluoroborate can act as X-site component to assemble ten instances of ABX3 molecular perovskites, only two of them possess hexagonal perovskite structures. Herein, we report two tetrafluoroborate-based hexagonal molecular perovskites, A[Na(BF4)3], by judiciously choosing two different A-site cations: 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium (Hmdabco2+) for 1 and 1-methylpiperazine-1,4-diium (H2mpz2+) for 2. They have high-temperature phases in the same space group (P63/mmc) revealing highly disordered A-site cations. Upon cooling, 1 undergoes two-step P63/mmc ↔ P3̅c1 ↔ P21/n transitions at 344 and 338 K, respectively, including a ferroelastic one (3̅mF2/m) accompanied by a spontaneous strain of 0.013. In contrast, the smaller H2mpz2+ cation with more adoptable conformations induces a one-step sharp P63/mmc ↔ P21/c ferroelastic transition (6/mmmF2/m(s)) at 418 K in 2, leading to more significant symmetry breaking and a considerable spontaneous strain of 0.129. This study provides important clues to modulate structural phase transitions by tuning diverse components for the multicomponent dense hybrid crystals.

Facile Solution-Refluxing Synthesis and Photocatalytic Dye Degradation of a Dynamic Covalent Organic Framework.

Covalent organic frameworks (COFs), as a novel crystalline porous adsorbent, have been attracting significant attention for their synthesis and application exploration due to the advantages of designability, stability, and functionalization. Herein, through increasing the concentration of the acid catalyst, a facile solution-refluxing synthesis method was developed for the preparation of a three-dimensional dynamic COF material, COF-300, with high yields (>90%) and high space−time yields (>28 kg m−3 day−1). This synthesis method not only permits gram-scale synthesis, but also yields products that well maintain porosity and unique guest-dependent dynamic behavior. Moreover, the catalytic activity of COF-300 as a metal-free photocatalyst was explored for the first time. Under 365 nm ultra-violet light irradiation, COF-300 can effectively catalyze the dye degradation (>99%) in wastewater with good recyclability. By adding magnetic Fe3O4 nanoparticles into the solution-refluxing synthesis of COF-300, Fe3O4/COF-300 nanocomposites can be obtained and used as magnetically recyclable photocatalysts, demonstrating the superiority of this facile synthesis procedure. Our study provides new insights for the preparation of COF materials and a constructive exploration for their water treatment application.

An Exceptional Thermally Induced Four-State Nonlinear Optical Switch Arising from Stepwise Molecular Dynamic Changes in a New Hybrid Salt.

Switching materials in channels of nonlinear optics (NLOs) are of particular interest in NLO material science. Numerous crystalline NLO switches based on structural phase transition have emerged, but most of them reveal a single-step switch between two different second-harmonic-generation (SHG) states, and only very rare cases involve three or more SHG states. Herein, we report a new organic-inorganic hybrid salt, (Me3 NNH2 )2 [CdI4 ], which is an unprecedented case of a reversible three-step NLO switch between SHG-silent, -medium, -low, and -high states, with high contrasts of 25.5/4.3/9.2 in a temperature range of 213-303 K. By using the combined techniques of variable-temperature X-ray single-crystal structural analyses, dielectric constants, solid-state 13 C nuclear magnetic resonance spectroscopy, and Hirshfeld surface analyses, we disclose that this four-state switchable SHG behavior is highly associated with the stepwise-changed molecular dynamics of the polar organic cations. This finding demonstrates well the complexity of molecular dynamics in simple hybrid salts and their potential in designing new advanced multistep switching materials.

Guest-Driven Light-Induced Spin Change in an Azobenzene Loaded Metal-Organic Framework.

Stimuli-responsive materials that can be reversibly switched by light are of immense interest. Among them, photo-responsive spin crossover (SCO) complexes have great promises to combine the photoactive inputs with multifaceted outputs into switchable materials and devices. However, the reversible control the spin-state change by photochromic guests is still challenging. Herein, we report an unprecedented guest-driven light-induced spin change (GD-LISC) in a Hofmann-type metal-organic framework (MOF), [Fe(bpn){Ag(CN)2 }2 ]⋅azobenzene. (1, bpn=1,4-bis(4-pyridyl)naphthalene). The reversible trans-cis photoisomerization of azobenzene guest upon UV/Vis irradiation in the solid-state results in the remarkable magnetic changes in a wide temperature range of 10-180 K. This finding not only establishes a new switching mechanism for SCO complexes, but also paves the way toward the development of new generation of photo-responsive magnetic materials.

[Degradation evaluation and success of pulpectomy with a modified primary root canal filling in primary molars].

OBJECTIVE: To compare clinical and radiographic success rates of a modified primary root canal filling (ingredients: zinc oxide-eugenol, iodoform and calcium hydroxide, MPRCF) vs. zinc oxide-eugenol cement (ZOE) and calcium hydroxide/iodoform paste (Vitapex) in pulpectomized primary molars at the end of 6 and 12 months, and to evaluate the degradation of materials in the root canals and in apical area. METHODS: In the study, 160 primary molars from 155 children (the average age: 5.88±1.27 years) that met the inclusion criteria were allocated to one of the three materials via block randomization. A two-visit pulpectomy was performed by an investigator. The clinical and radiographic diagnoses were blindly assessed by other two investigators. RESULTS: At the end of 6 and 12 months, the ZOE and MPRCF success rates were 100% both in clinical and radiographic evaluation. The Vitapex group showed the clinical success of 100% at the end of 6 months and 94.5% at the end of 12 months. Radiographic evaluation for the Vitapex group showed 80.4% success at the end of 6 months and 60.7% at the end of 12 months. No statistically significant differences were noted at the end of 6 months in the three groups both in clinical and radiographic evaluation. The success rates in clinical and radiographic evaluation at the end of 12 months for ZOE and MPRCF groups were not significantly different, and better than those for Vitapex group with statistically significant difference. The completely resorb rate of excess extruded extraradicularly were 14.3%, 100% and 71.4% for ZOE, Vitapex and MPRCF at the end of 12 months. The rates of resorption of material at the same rate of the root were 5.8%, 7.2% and 40.9% for ZOE, Vitapex and MPRCF at the end of 12 months. CONCLUSION: MPRCF, a mixture of zinc oxide eugenol and iodoform with calcium hydroxide can be used as a root canal filling material in primary teeth, taking account of the success rate and resorbing at a similar rate with the roots of the primary teeth.

[Influence of the effect of general anaesthesia and restraint during dental treatment on dental anxiety and behavior in children].

OBJECTIVE: To compare the level of dental anxiety and dental behavior between dental fear children with dental treatment under general anaesthesia (GA) and those under restraint. METHODS: The GA group included 31 dental fear children aged 4-6-year-old who received dental treatment under the GA. The restraint group included 31 dental fear children aged 4-6-year-old who received dental treatment under the restraint. Age, gender, parent's education level, decayed-missing-filled-tooth (dmft) and face version of the Modified Child Dental Anxiety Scale (MCDASf) score before treatment were matched between the two groups. The Chinese version of MCDASf was used to evaluate the level of dental anxiety in each child before treatment, right after treatment and before examination at recall visit 2-3 weeks after treatment. And the Chinese version of Venham Clinical Anxiety and Cooperative Behavior Scale was used to evaluate children's dental behavior in each child before treatment and before examination at recall visit 2-3 weeks after treatment. RESULTS: The average scores of MCDASf in GA group right after treatment and before recall were lower than that before treatment. The difference was statistically significant (P<0.05). Furthermore, the average score of MCDASf before recall was lower than those after treatment, and the difference was statistically significant (P<0.05). The average scores of MCDASf in restraint group right after treatment and 2-3 weeks after treatment were higher than those before treatment, but the difference was not statistically significant (P>0.05). Children's dental behavior was significantly improved at recall visit in both groups (P<0.01). CONCLUSION: Dental fear could be reduced by treatment under GA. The children's dental behavior was improved after GA. Restraint did not result in the significant elevation of dental anxiety level, but dental behavior was improved after restraint during the short-term recall.

Designing dynamic coordination bonds in polar hybrid crystals for a high-temperature ferroelastic transition.

Ferroelastic materials have gained widespread attention as promising candidates for mechanical switches, shape memory, and information processing. Their phase-transition mechanisms usually originate from conventional order-disorder and/or displacive types, while those involving dynamic coordination bonds are still scarce. Herein, based on a strategic molecular design of organic cations, we report three new polar hybrid crystals with a generic formula of AA'RbBiCl6 (A = A' = Me3SO+ for 1; A = Me3SO+ and A' = Me4N+ for 2; A = A' = Me3NNH2+ for 3). Their A-site cations link to the [RbBiCl6]n2n- inorganic framework with lon topology through Rb-O/N coordination bonds, while their significantly different interactions between A'-site cations and inorganic frameworks provide distinct phase-transition behaviour. In detail, the strongly coordinative A'-site Me3SO+ cations prevent 1 from a structural phase transition, while coordinatively free A'-site Me4N+ cations trigger a conventional order-disorder ferroelastic transition at 247 K in 2, accompanied by a latent heat of 0.63 J g-1 and a usual "high → low" second-harmonic-generation (SHG) switch. Interestingly, the A'-site Me3NNH2+ cations in 3 reveal unusual dynamic coordination bonds, driving a high-temperature ferroelastic transition at 369 K with a large latent heat of 18.34 J g-1 and an unusual "low → high" SHG-switching behaviour. This work provides an effective molecular assembly strategy to establish dynamic coordination bonds in a new type of host-guest model and opens an avenue for designing advanced ferroelastic multifunctional materials.

Heat- and Pressure-driven Room-temperature Polymorphic Transition Accompanied with Switchable SHG Signal in a New Chiral Hexagonal Perovskite.

Endowing room-temperature polymorphs with both long-term stability and easy interconvertibility is a big challenge due to the complexity of intermolecular interactions. Herein, we present a chiral hexagonal perovskite (R-3-hydroxy-1-methylpiperidinium)[CdCl3 ] having two room-temperature crystalline forms featuring obviously distinct second-harmonic-generation (SHG) signals with a high switching contrast of ~18 times. The two room-temperature forms could be long-term stable yet easily interconvertible through an irreversible thermal-induced phase transition and a pressure-driven backward transition, by switching hydrogen bonds via collective reorientation of ordered homochiral cations. Based on the essential role of homochiral organic cations in inducing switchable hydrogen bond linkages, this present instance provides good evidence that relatively irregular organic cations could induce more obvious inorganic chain deformations, thus endowing polymorphs with significantly different SHG signals at room temperature.

An anomalous ferroelastic phase transition arising from an unusual cis-/anti-conformational reversal of polar organic cations.

Hybrid ferroelastics have attracted increasing attention for their potential application as mechanical switches. The sporadically documented anomalous ferroelastic phase transitions, i.e., ferroelasticity that appears at a high-temperature phase rather than a low-temperature phase, are of particular interest but are not well understood at the molecular level. By judiciously choosing a polar and flexible organic cation (Me2NH(CH2)2Br+) with cis-/anti- conformations as an A-site component, we obtained two new polar hybrid ferroelastics, A2[MBr6] (M = Te for 1 and Sn for 2). These materials undergo distinct thermal-induced ferroelastic phase transitions. The larger [TeBr6]2- anions anchor the adjacent organic cations well and essentially endow 1 with a conventional ferroelastic transition (P21 → Pm21n) arising from a common order-disorder transition of organic cations without conformational changes. Moreover, the smaller [SnBr6]2- anions can interact with the adjacent organic cations in energetically similar sets of intermolecular interactions, enabling 2 to undergo an anomalous ferroelastic phase transition (P212121 → P21) arising from an unusual cis-/anti-conformational reversal of organic cations. These two instances demonstrate the importance of the delicate balance of intermolecular interactions for inducing anomalous ferroelastic phase transitions. The findings here provide important insights for seeking new multifunctional ferroelastic materials.

Periodate-based molecular perovskites as promising energetic biocidal agents.

Epidemics caused by pathogens in recent years have created an urgent need for energetic biocidal agents with the capacity of detonation and releasing bactericides. Herein we present a new type of energetic biocidal agents based on a series of iodine-rich molecular perovskites, (H2dabco)M(IO4)3 (dabco = 1,4-diazabicyclo[2.2.2]octane, M = Na+/K+/Rb+/NH4 + for DAI-1/2/3/4) and (H2dabco)Na(H4IO6)3 (DAI-X1). These compounds possess a cubic perovskite structure, and notably have not only high iodine contents (49-54 wt%), but also high performance in detonation velocity (6.331-6.558 km s-1) and detonation pressure (30.69-30.88 GPa). In particular, DAI-4 has a very high iodine content of 54.0 wt% and simultaneously an exceptional detonation velocity up to 6.558 km s-1. As disclosed by laser scanning confocal microscopy observation and a standard micro-broth dilution method, the detonation products of DAI-4 exhibit a broad-spectrum bactericidal effect against bacteria (E. coli, S. aureus, and P. aeruginosa). The advantages of easy scale-up synthesis, low cost, high detonation performance, and high iodine contents enable these periodate-based molecular perovskites to be highly promising candidates for energetic biocidal agents. Electronic Supplementary Material: Supplementary material is available in the online version of this article at 10.1007/s40843-022-2257-6.

A reaction rate measurement experimental program of China experimental fast reactor.

The study of the nuclear reaction rate distribution in the MOX core of China Experimental Fast Reactor is a necessary condition for obtaining the operating license. From the characteristics of core structure, both the principle of experimental and experimental system are studies, emphasized on the scheme design such as the size of foils, the irradiation power and counting rate. Firstly, based on the Monte Carlo Code（MCNP）and NJOY codes, the distribution of reaction rates is obtained. MCNP is a general-purpose Monte Carlo N-Particle code that can be used for neutron, photon, electron, and so on. The NJOY nuclear data processing system is a comprehensive computer code package for producing to cross sections and related nuclear parameters from ENDF/B VIII.0 evaluated nuclear data. Secondly, the activity measurement of foils was obtained by HPGE, then the reaction rate is determined by data processing. It is worth mentioning that the experimental reactivity introduction has a negligible effect on the reactor core by MCNP. Finally, a set of activation experiment scheme that is suitable for CEFR MOX core is formed, which serves as a guide to carry out activation method experiments.

Subtly tuning intermolecular hydrogen bonds in hybrid crystals to achieve ultrahigh-temperature molecular ferroelastic.

Molecular-based ferroic phase-transition materials have attracted increasing attention in the past decades due to their promising potential as sensors, switches, and memory. One of the long-term challenges in the development of molecular-based ferroic materials is determining how to promote the ferroic phase-transition temperature (T c). Herein, we present two new hexagonal molecular perovskites, (nortropinonium)[CdCl3] (1) and (nortropinium)[CdCl3] (2), to demonstrate a simple design principle for obtaining ultrahigh-T c ferroelastic phase transitions. They consist of same host inorganic chains but subtly different guest organic cations featuring a rigid carbonyl and a flexible hydroxyl group in 1 and 2, respectively. With stronger hydrogen bonds involving the carbonyl but a relatively lower decomposition temperature (T d, 480 K), 1 does not exhibit a crystalline phase transition before its decomposition. The hydroxyl group subtly changes the balance of intermolecular interactions in 2via reducing the attractive hydrogen bonds but increasing the repulsive interactions between adjacent organic cations, which finally endows 2 with an enhanced thermal stability (T d = 570 K) and three structural phase transitions, including two ferroelastic phase transitions at ultrahigh T c values of 463 K and 495 K, respectively. This finding provides important clues to judiciously tuning the intermolecular interactions in hybrid crystals for developing high-T c ferroic materials.

An unprecedented hexagonal double perovskite organic-inorganic hybrid ferroelastic material: (piperidinium)2[KBiCl6].

An unprecedented A2MIMIIIX6-type double perovskite adopting a fully hexagonal BaNiO3-type structure, (piperidinium)2[KBiCl6], undergoes a 2/mF1[combining macron] ferroelastic phase transition at 285 K with a spontaneous strain of 0.0615, arising from the order-disorder transition of organic cations together with the synchronous displacement of inorganic chains.

Room-temperature ferroelectric and ferroelastic orders coexisting in a new tetrafluoroborate-based perovskite.

The coexistence of multiferroic orders has attracted increasing attention for its potential applications in multiple-state memory, switches, and computing, but it is still challenging to design single-phase crystalline materials hosting multiferroic orders at above room temperature. By utilizing versatile ABX3-type perovskites as a structural model, we judiciously introduced a polar organic cation with easily changeable conformations into a tetrafluoroborate-based perovskite system, and successfully obtained an unprecedented molecular perovskite, (homopiperazine-1,4-diium)[K(BF4)3], hosting both ferroelectricity and ferroelasticity at above room temperature. By using the combined techniques of variable-temperature single-crystal X-ray structural analyses, differential scanning calorimetry, and dielectric, second harmonic generation, and piezoresponse force microscopy measurements, we demonstrated the domain structures for ferroelectric and ferroelastic orders, and furthermore disclosed how the delicate interplay between stepwise changed dynamics of organic cations and cooperative deformation of the inorganic framework induces ferroelectric and ferroelastic phase transitions at 311 K and 455 K, respectively. This instance, together with the underlying mechanism of ferroic transitions, provides important clues for designing advanced multiferroic materials based on organic-inorganic hybrid crystals.

Nitroprusside as a promising building block to assemble an organic-inorganic hybrid for thermo-responsive switching materials.

We present a new hybrid compound, namely (Me2NH2)[KFe(CN)5(NO)], possessing a unique nitroprusside-based inorganic host framework in 4-connected sra topology encapsulating organic guest cations. The flexible host-guest hydrogen bonds and synchronously deformed inorganic framework give rise to thermal-responsive switching behaviours on both thermal expansion and nonlinear optical properties during the phase transition at around room temperature.

Enhancing switchable dielectric property for crystalline supramolecular rotor compounds by adding polar components.

Two new compounds were obtained by assembling the [(2-methoxy-5-nitro-anilinium)(18-crown-6)]+ cation with non-polar PF6- and polar SO3CF3- anions, respectively. Benefiting from its polar anion, the SO3CF3- compound reveals a more significant dielectric switching behaviour during phase transition, demonstrating an effective strategy to enhance the dielectric property by adding polar components.

Clinical comparison of Fuji VII and a resin sealant in children at high and low risk of caries.

The purpose was to compare the retention and caries preventive effect of Fuji VII and a resin-based sealant in children at high risk (HR) and low risk (LR) of caries. Fifty-seven schoolchildren (150 teeth) with completely erupted bilateral permanent first molars were included. The study was a split-mouth, randomized trial. Sealant retention and caries were evaluated after 6 months, 1 year and 2 years. After 2 years, there was no statistically significant difference in the incidence of caries between Fuji VII and Concise in the HR and LR groups. With Concise, LR children were less likely to have dental caries than HR. With Fuji VII, there was no difference in caries incidence between LR and HR. Retention of Concise was superior to that of Fuji VII. Our results suggest that Fuji VII and Concise sealants had similar caries preventive effects in children at high and low risk of caries.