Negative linear compressibility and strong enhancement of emission in Eu[Ag(CN)2]3·3H2O under pressure.

The framework material Eu[Ag(CN)2]3·3H2O exhibits a negative linear compressibility (NLC) of -4.2(1) TPa-1 over the largest pressure range yet observed (0-8.2 GPa). High-pressure single-crystal X-ray diffraction data show that the rapid contraction of the Kagome silver layers under compression causes the wine-rack lattice to expand along the c-axis. The hydrogen bonds between the water molecules and the main frameworks constrain the structural deformation under pressure and eventually a weak NLC effect generated. Furthermore, we found that the pressure-induced emission intensity increases almost 800-fold at 4.0 GPa, followed by a gradual decrease and disappearance at 8.1 GPa. Under compression, high pressure significantly tunes the triplet level positions near the Eu3+ ions, and horizontal displacement between a quenching excited state and the excited levels of Eu3+ facilitates the energy transfer process to the 5D0 excited state and limits the nonradiative corssover at elevated pressures, thus increasing the emission intensity. In addition, we observe a gradual band gap reduction with increasing pressure, and the sample could not be returned to the initial state after the pressure was completely released. By controlling the structural flexibility, we observe a coupled NLC and pressure-induced strong enhancement of the emission properties of Eu[Ag(CN)2]3·3H2O, which provides a new route for the design of new optical devices with intriguing luminescence properties under extreme environments.

A Versatile Metalloporphyrinic Framework Platform for Highly Efficient Bioinspired, Photo- and Asymmetric Catalysis.

Even though numerous bioinspired catalysts have been developed, there remain huge gaps between the artificial and natural catalysts, because it is very difficult to imitate simultaneously the complicated constituents, structures, and synergistic effect of enzymes. We report herein a versatile metalloporphyrinic framework platform, which exhibits high efficiency in bioinspired catalysis, photocatalysis, and asymmetric catalysis. The catalytic properties are highly dependent on the tunable constituents and their cooperation, and are significantly superior to the corresponding molecular catalyst systems which lack the synergistic effects. Since there are numerous functional moieties that can readily be incorporated into the metalloporphyrinic framework platform, a myriad of applications can be simply realized by embedding different functional moieties.

Assembly of a Metalloporphyrin-Polyoxometalate Hybrid Material for Highly Efficient Activation of Molecular Oxygen.

Organic metalloporphyrins and inorganic polyoxometalates (POMs) are two kinds of efficient molecular catalysts to prompt a variety of chemical reactions. They have been used as active moieties for the synthesis of porous materials to realize highly efficient heterogeneous catalysis. Both of them are regarded as the organic/inorganic equivalent counterparts to complement the individual features. Therefore, the combination of metalloporphyrins and POMs in the same hybrid materials might generate interesting catalytic properties by emerging their unique individual functions. To avoid the random connections between metalloporphyrins, POMs, and lanthanide connecting nodes, we have developed a "step-by-step" aggregation strategy, including the reaction of POMs with metal ions to bind metal nodes on the surfaces of POMs at the first step and the reaction of the resulting POM derivatives with metalloporphyrin linkers to result in hybrid materials at the second step. Catalytic experiments demonstrate that the resulting hybrid material exhibits interesting catalytic properties in the heterogeneous epoxidation of olefins, in which the conversion, epoxide selectivity, turnover number, and turnover frequency for the epoxidation of styrene to (1,2-epoxyethyl)benzene are >99%, 94%, 220000, and 22000 h(-1), respectively. These results demonstrate that the collaborative work of multiple active sites in hybrid materials can achieve superior high efficiency in heterogeneous catalysis.

Effect of phosphate rock acid insoluble residue on hydration process and mechanical properties of α-hemihydrate gypsum.

The application of α-hemihydrate gypsum (α-HH) is limited by several factors, such as a rapid hydration rate, short setting time, poor water resistance, and high cost. Especially because of the high production cost, although α-HH has excellent mechanical strength, it is rarely used in the field of building materials. In this study, based on the composition characteristics of new industrial solid waste (phosphate-rock acid-insoluble residue, PAIR) and to meet the needs of resource utilization, gypsum matrix composites were prepared by adding PAIR to α-HH to solve the problems of short setting time and poor water resistance of gypsum matrix composites and improve the comprehensive properties of α-HH products. The results show that when the different types of pores formed during the hydration of α-HH were filled with inert substances, such as silicon dioxide, insoluble phosphate, and calcium fluoride from PAIR, the proportion of mesopores in the composite products increased, whereas that of harmful macropores decreased. The compressive and flexural softening coefficients of the PAIR/α-HH system with 23% PAIR were the highest at 57.25 and 60.125%, respectively, and the water resistance of the system was improved; when the content of PAIR reaches 35%, the strength of the composite products decreased from 58.125 to 43.8 MPa. The HPO42- in PAIR partially replaces the SO42- ion in the dihydrate gypsum (DH) lattice to form a Ca(SO4, HPO4)•2H2O double salt, leading to the production of eutectic phosphorus. Soluble F-, Al3+, Mg2+, and phosphorus-containing substances in PAIR form a variety of complex ions in PAIR/α-HH aqueous solution, which are adsorbed onto the surface of the new DH phase; the crystal morphology changed from thick, long columns to clusters, thin rods, and plates, inhibiting the nucleation and growth of DH and changing its crystal growth rate and crystallization behavior. Therefore, the setting time of gypsum is prolonged; when 35% PAIR was added, the induced nucleation period of the PAIR/α-HH system was prolonged from 40 to 265 min, and the final setting time was from 12 to 360 min. By mixing solid waste PAIR, while the setting time of α-HH is prolonged, its water resistance is improved, and its mechanical strength is not significantly reduced, reducing the cost. From the perspective of economy and environmental protection, this study is a way to α-HH is widely used in the field of building materials.

Kinetic and thermodynamic analysis on preparation of belite-calcium sulphoaluminate cement using electrolytic manganese residue and barium slag by TGA.

Electrolytic manganese residue (EMR) is a solid filter residue obtained from manganese carbonate ore during the production of metal manganese. A potential avenue towards large-scale utilisation of EMR is its use in cement preparation. However, the preparation of cement materials using EMR requires high-temperature calcination. In this study, the thermal properties and pyrolysis kinetics of belite-calcium sulfoaluminate cement raw meal were systematically studied using a multiple-heating-rate method based on thermogravimetric analysis and a kinetic model. The kinetic and thermodynamic parameters was studied using non-isothermal Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), Friedman and Kissinger methods. The results showed that from 30 to 1300°C, the pyrolysis reaction of cement raw meal was mainly divided into four steps: the crystalline water removal from calcium sulphate dihydrate and bauxite, the ammonia nitrogen removal from ammonium salts and the calcium sulphate crystal transformation; the decomposition of calcium carbonate and carbon-containing organic matter; the sulphate and carbonate substance decomposition and the clinker mineral phase formation. The average activation energies calculated when using the non-isothermal FWO, KAS, Friedman and Kissinger methods were 244.49, 240.7, 239.24 and 380.60 kJ/mol and the average pre-exponential factors were 1.75 × 1020, 3.65 × 1020, 7.11 × 1021 and 1.55 × 1013 s-1, respectively. Herein, the pyrolysis kinetics of the cement raw meal was divided into two main stages: In stage 1 (α: 0.15-0.8, 524°C-754°C), the mechanism of P2/3 accelerated nucleation in the Mampel Power rule, and the reaction mechanism function was G(α)=α3/2. In stage 2 (α: 0.80-0.95, 754°C-1165°C), during the local conversion of α = 0.2-0.8, when α was <0.5, the chemical reaction mechanism of the R3 phase boundary was noted and the mechanism function was G(α) = 1 - (1-α)1/3; however, when α was >0.5, a random nucleation and subsequent growth mechanism of A6 was noted and the mechanism function was G(α) = [-ln(1 - α)]2/3.

Study on mutual harmless treatment of electrolytic manganese residue and red mud.

Electrolytic manganese residue (EMR) and red mud (RM) are solid waste by-products of the metal manganese and alumina industries, respectively. Under long-term open storage, ammonia nitrogen and soluble manganese ions in EMR and alkaline substances in RM severely pollute and harm the environment. In order to alleviate the pollution problem of EMR and RM. In this study, the alkaline substances in RM were used to treat ammonia nitrogen and soluble manganese ions in EMR. The results confirm the following suitable treatment conditions for the mutual treatment of EMR and RM: EMR-RM mass ratio = 1:1, liquid-solid ratio = 1.4:1, and stirring time = 320 min. Under these conditions, the elimination ratios of ammonia nitrogen (emitted in the form of ammonia gas) and soluble manganese ions (solidified in the form of Mn3.88O7(OH) and KMn8O16) are 85.87 and 86.63%, respectively. Moreover, the alkaline substances in RM are converted into neutral salts (Na2SO4 and Mg3O(CO3)2), achieving de-alkalinisation. The treatment method can also solidify the heavy metal ions-Cr3+, Cu2+, Ni2+, and Zn2+-present in the waste residue with leaching concentrations of 1.45 mg/L, 0.099 mg/L, 0.294 mg/L, and 0.449 mg/L, respectively. This satisfies the requirements of the Chinese standard GB5085.3-2007. In the mutual treatment of EMR and RM, the kinetics of ammonia nitrogen removal and manganese-ion solidification reactions are controlled via a combination of membrane diffusion and chemical reaction mechanisms.

Pressure-Induced Ferroelastic Transition Drives a Large Shape Change in a Ni(II) Complex Single Crystal.

Crystals with significant length reduction at an accessible low pressure are highly desirable for piezo-responsive devices. Here, we show a molecular crystal [Ni(en)3](ox) (en = ethylenediamine and ox = oxalate anion) that exhibits an abrupt shape change with a contraction rate of ∼4.7% along its c axis near the phase transition pressure of ∼0.2 GPa. High-pressure single-crystal X-ray diffraction and Raman spectroscopy measurements reveal that this material undergoes a first-order ferroelastic transition from high-symmetry trigonal P3̅1c to low-symmetry monoclinic P21/n at ∼0.2 GPa. The oxalate anions serve as unique components, and their disorder-order transformation and rotation of 90° through cooperative intermolecular hydrogen bonding triggered unconventional anisotropic microsize contraction under compression, which can be appreciated visually. Such a prominent directional deformation at a low pressure driven by molecular motors of oxalate anions provides insights for the design of novel molecular crystal-based piezo-responsive switches and actuators in deep-sea environments.

Ultrasound programmable hydrogen-bonded organic frameworks for sono-chemogenetics.

The precise control of mechanochemical activation within deep tissues via non-invasive ultrasound holds profound implications for advancing our understanding of fundamental biomedical sciences and revolutionizing disease treatments. However, a theory-guided mechanoresponsive materials system with well-defined ultrasound activation has yet to be explored. Here we present the concept of using porous hydrogen-bonded organic frameworks (HOFs) as toolkits for focused ultrasound programmably triggered drug activation to control specific cellular events in the deep brain, through on-demand scission of the supramolecular interactions. A theoretical model is developed to visualize the mechanochemical scission and ultrasound mechanics, providing valuable guidelines for the rational design of mechanoresponsive materials at the molecular level to achieve programmable and spatiotemporal activation control. To demonstrate the practicality of this approach, we encapsulate designer drug clozapine N-oxide (CNO) into the optimal HOF nanoparticles for FUS gated release to activate engineered G-protein-coupled receptors in the mice and rat ventral tegmental area (VTA), and hence achieved targeted neural circuits modulation even at depth 9 mm with a latency of seconds. This work demonstrates the capability of ultrasound to precisely control molecular interaction and develops ultrasound programmable HOFs to minimally invasive and spatiotemporally control cellular events, thereby facilitating the establishment of precise molecular therapeutic possibilities. We anticipate that this research could serve as a source of inspiration for precise and non-invasive molecular manipulation techniques, potentially applicable in programming molecular robots to achieve sophisticated control over cellular events in deep tissues.

Thermal properties and pyrolysis kinetics of phosphate-rock acid-insoluble residues.

In the phosphorous-sulphur two-step process for the clean production of phosphoric acid, a phosphate-rock acid-insoluble residue (PAIR) is a solid filter residue obtained via the phosphoric acid acidolysis of phosphate rock (PR). PAIR combined with other raw materials can be used to prepare cement, ceramics and glasses, opening a potential avenue for large-scale PAIR utilisation. However, the preparation of such materials requires high-temperatures calcination. Understanding the high-temperature thermal properties of PAIR can enable its more targeted comprehensive utilisation or disposal. In this study, the thermal properties and pyrolysis kinetics of PAIR were systematically studied using a multiple heating rate method based on thermogravimetric analysis and a kinetic model. Results showed that from room temperature to 1200 °C, the main changes in the PAIR were the complete removal of fluorine and sulphur, partial removal of phosphorus and conversion of quartz to cristobalite. Moreover, during these processes, H2O(g), NH3, N2, CO2, SO2, P2O5(g), CO, CF3+ and organic gases were volatilised. Herein, the pyrolysis kinetics of PAIR is divided into five stages. Stage 1 (conversion rate ɑ: 0.05-0.2) conforms to the random nucleation and growth as well as the Avrami-Erofeev (n = 2/3) mechanism; the corresponding mechanism function is F(ɑ) = [-Ln(1 - ɑ)]2/3. Stage 2 (ɑ: 0.2-0.4) conforms to the first-order chemical reaction mechanism; the corresponding mechanism function is F(ɑ) = -Ln(1 - ɑ). Stage 3 (ɑ: 0.4-0.6) conforms to the phase boundary-controlled reaction and one-dimensional movement mechanism; the corresponding mechanism function is F(ɑ) = ɑ. Stage 4 (ɑ: 0.6-0.8) conforms to the three-dimensional diffusion process (Jander model); the corresponding mechanism function is F(ɑ) = [1 - (1 - ɑ)1/3]2. Stage 5 (ɑ: 0.6-0.95) conforms to the one-dimensional diffusion process; the corresponding mechanism function is F(ɑ) = ɑ2.

Existing form and distribution of fluorine and phosphorus in phosphate rock acid-insoluble residue.

The phosphorus-sulfur two-step production process was developed in the wet-process phosphoric acid industry to solve phosphogypsum pollution. However, phosphate rock acid-insoluble residue is produced during this process as a new type of solid waste, which had a high potential for recycling. For process reasons, this type of residue still contains a certain amount of fluorine and phosphorus, which has a massive impact on the potential uses of phosphate rock acid-insoluble residue. Therefore, X-ray photoelectron spectroscopy, Raman, electron probe spectroscopy, and scanning electron microscopy were used to examine the existing form and distribution of fluorine and phosphorus in phosphate rock acid-insoluble residue. The mass fraction of F and P2O5 were 9.407% and 11.862%, respectively. Fluorine existed mainly in the form of fluorite, fluorapatite and metal fluoride. Phosphorus existed mainly in the form of fluoroapatite, phosphate, hydrogen phosphate, and dihydrogen phosphate. The total phosphate, hydrogen phosphate and dihydrogen phosphate contents were much higher than that of fluoroapatite, whereas the fluoroapatite content was higher than that of fluorite and metal fluoride. Fluorine and phosphorus were distributed in the form of agglomerates in the phosphate rock acid-insoluble residue. Fluorine and phosphorus were partially correlated, showing a weak relationship in the high phosphorus area.

[Validity of inquiry in screening chronic schistosomiasis japonica].

OBJECTIVE: To study the indicators and validity of inquiry in the screening of chronic schistosomiasis japonica. METHODS: 51 villages of Hanshou county were selected at random in Hunan Province and the whole resident (>6 months/year) population aged 5 years and above was eligible for inclusion in the study. Inquiry through questionnairing, serological test (ELISA) and B type ultrasonography were applied respectively to screen chronic cases and evaluate morbidity due to schistosome infection. Logistic analysis was performed to explore the relationship between indicators of questionnaire and the results of ELISA and abdominal ultrasonography. Bayes discriminant analysis was used to assess consistency of inquiry and ELISA, inquiry and the degree of hepatic fibrosis. RESULTS: 26,426 inhabitants in the endemic villages were screened by ELISA with 1380 (5.2%) positive. 1264 sero-positive and 1446 sero-negative cases were asked questions relating to schistosomiasis and examined by abdominal ultrasonography. Inquiry indices such as self-reported diarrhea, stool with mucus and fatigue during the last two weeks, history of infested water contact and times of treatment were specific to chronic schistosomiasis. The coincident rate for validation was 75.9% between inquiry and ELISA, and 75.4% between inquiry and hepatic fibrosis degree. CONCLUSION: Validity of inquiry was satisfactory in screening chronic schistosomiasis in endemic areas.

[Establishment and application of spatio-temporal model of schistosomiasis japonica in a county in marshland region].

OBJECTIVE: To develop a spatio-temporal model of schistosomiasis japonica based on Bayesian model, and to analyze the spatio-temporal pattern of schistosomiasis, as well as to evaluate the impact of environment changes on schistosomiasis endemic. METHODS: Different Bayesian models were established by employing the data of the periodical surveillance on schistosomiasis during 1996-2005 period by taking into account of the uncertainty in sensitivity and specificity of diagnostic test, then the best fitness model was selected to analyze the spatio-temporal pattern of schistosomiasis and evaluate the impact of environment changes on schistosomiasis. RESULTS: The model with space-time interaction was a better fitting model. No significant temporal correlation was found in human infection rate of Schistosoma japonicum, and the difference of spatial structure between human infection rates of each year was significant. The prediction map of S. japonicum infection showed the changes of infection in the south areas of the Yuan River were not significant, while the prevalence increased significantly in the north areas of the river, which indicated that the impact of the implementation of project on partial abandon areas for water storing on prevalence of S. japonicum was stronger than that of the project on completed abandon areas for water storing. CONCLUSIONS: It is feasible to develop the spatio-temporal model of schistosomiasis japonica based on Bayesian model, and this inetegrated Bayesian model approach may become a powerful and statistically robust tool for estimating and evaluating the control strategy.