Effects of Hydration on the Adsorption of Benzohydroxamic Acid on the Lead-Ion-Activated Cassiterite Surface: A DFT Study.

The strategy of enhancing the surface activity by preadsorption of metal ions (surface activation) is an effective way to promote the adsorption of surfactant on surfaces, which is very important in surface process engineering. However, the adsorption mechanism of surfactant (collector) on the surface preadsorbed by metal ions in the explicit solution phase is still poorly understood. Herein, the effects of hydration on the adsorption of benzohydroxamic acid (BHA) onto the oxide mineral surface before and after lead-ion activation are investigated by first-principles calculations, owing to its importance in the field of flotation. The results show that the direct adsorption of BHA on the hydrated surface is not thermodynamically allowed in the absence of metal ions. However, the adsorption of BHA onto the lead-ion-activated surface possesses a very low barrier and a very negative reaction energy difference, indicating that the adsorption of BHA on hydrated Pb2+ at cassiterite surface is very favorable in both thermodynamics and kinetics. In addition, the adsorption of BHA results in the dehydration of hydrated Pb2+. More interestingly, the surface hydroxyl groups could participate in and may promote the coordination adsorption through proton transfer. This work sheds some new lights on understanding the roles of interfacial water and the mechanisms of metal-ion surface activation.

Effects of the Goethite Surface Hydration Microstructure on the Adsorption of the Collectors Dodecylamine and Sodium Oleate.

Dodecylamine (DDA) and sodium oleate (OL) are commonly used collectors in the reverse flotation and the direct flotation of goethite. However, the flotation mechanisms of DDA and OL on the goethite surface remain unclear. In this study, the first-principles density functional theory calculations were used to reveal the role of the hydration of the goethite surface and its effects on flotation reagents from a microscopic perspective. The calculation results showed that DDA was adsorbed on the surface of goethite by hydrogen bonds in the absence of hydration. However, the existence of the hydration microstructure hindered the formation of hydrogen bonds and made it difficult for DDA to be adsorbed on the goethite surface. In the OL system, oleate ions are chemically adsorbed on the surface Fe sites of goethite in the absence of hydration, while in the presence of hydration, the oleate ions were adsorbed on the H-terminal hydration surface of goethite by hydrogen bonds. This work sheds new light on the roles of the hydration microstructure and the adsorption mechanism of the flotation reagent on the oxide minerals.

Interface Interaction of Benzohydroxamic Acid with Lead Ions on Oxide Mineral Surfaces: A Coordination Mechanism Study.

Surface coordination chemistry is important in areas such as adsorption, separation, and catalysts. In this work, surface coordination interactions of benzohydroxamic acid (BHA) with the lead ion [Pb(II)] adsorbed on the cassiterite surface have been investigated by first-principles calculations due to its great significance in froth flotation. Cluster calculations show that BHA possesses the weakest chelation with Pb(II) due to the electron withdrawal ability of the benzyl ring in comparison with other hydroxamic acids. Pb(II) thermodynamically prefers to react with the cassiterite surface rather than BHA. On the other hand, the partial density of states and the atomic overlap populations have consistently verified that the adsorption of BHA results in a better symmetry in electron densities than the hydrated Pb(II). The electron density maps and the electronic localization functions have further visualized the rearrangement of the 6s2 lone pair around the lead atom. It can be concluded that the surface coordination mechanisms of Pb(II) on oxide minerals can be attributed to the coordination ability of BHA and the unique electronic structure of Pb(II), which accounts for the reported better flotation performance of the pre-assemble strategy than the pre-activating approach. This work sheds some new light on the unique coordination activation mechanism of metal ions on oxide mineral surfaces. It should be instructive to design and screen new environment-friendly flotation reagents and flotation flowsheets.

Adsorption Mechanism of 4-Amino-5-mercapto-1,2,4-triazole as Flotation Reagent on Chalcopyrite.

A novel compound 4-amino-5-mercapto-1,2,4-triazole was first synthesized, and its selective adsorption mechanism on the surface of chalcopyrite was comprehensively investigated using UV-vis spectra, zeta-potential, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy measurements (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and first principles calculations. The experimental and computational results consistently demonstrated that AMT would chemisorb onto the chalcopyrite surface by the formation of a five-membered chelate ring. The first principles periodic calculations further indicated that AMT would prefer to adsorb onto Cu rather than Fe due to the more negative adsorption energy of AMT on Cu in the chalcopyrite (001) surface, which was further confirmed by the coordination reaction energies of AMT-Cu and AMT-Fe based on the simplified cluster models at a higher accuracy level (UB3LYP/Def2-TZVP). The bench-scale results indicated that the selective index improved significantly when using AMT as a chalcopyrite depressant in Cu-Mo flotation separation.

Insights into the Fracture Nature of Hematite from First Principles DFT Calculations.

Hematite, as an important iron source, usually crystallizes in the structure of rhombohedral R3̅c in nature. To date, reports on the major exposed surface of hematite are still inconclusive. Herein, the fracture nature of hematite is studied by the density functional theory (DFT) method. The fracture surface morphology analysis predicts the fracture dominance of the (012) plane structurally. Besides, the lowest surface broken bond density (D b) and the surface energy among all of the investigated surfaces also establish the exposure priority of the (012) surface. In addition, the (110) and (104) surfaces also show a strong fracture potential. In our proposed partition model, the exposure priority of (110) and (104) surfaces in region 2 with a lower surface energy and surface broken bond density is second only to the (012) surface. The other surfaces, except for the (012), (110), and (104) surfaces, are divided into region 3; here, the exposure of the surfaces located in this region is considered to be uncompetitive.

Chitosan-induced self-assembly of montmorillonite nanosheets along the end-face for methylene blue removal from water.

In this study, chitosan-induced self-assembly of montmorillonite nanosheets (MMTNS) along the end-face to form the layered and porous structured composite with high adsorption capacity towards MB dye wastewater was investigated. The self-assembly process was driven by the hydrogen-bond interaction among -OH groups distributed along the end-face of MMTNS and -NH2 groups on chitosan (CS) chain, which finally formed the infinite two-dimensional lamellae. This technology remained the exposed adsorption sites on MMTNS surface, and solved the separation issue of spent MMTNS from water, making MMTNS/CS an excellent adsorption material for macromolecular MB dye. The maximum adsorption capacity of MMTNS/CS towards MB reached 243 mg/g, which was achieved via the Na+- exchange, hydrogen-bond and n-π stacking interactions with MB molecules. This work aimed at breaking through the bottleneck of small adsorption capacity of traditional MMT adsorbents, solving the problem of solid-liquid separation of nanosheets, and effectively reducing the adsorption cost, which might guide an important direction for adsorption material design and development in the future.

Effect of novel stabilizers--cationic polymers on the particle size and physical stability of poorly soluble drug nanocrystals.

In this study, a novel class of stabilizer, cationic polymer, was introduced into the system of nanocrystals. Taking itraconazole as a poorly soluble model drug, the influence of three cationic polymers-chitosan, N-trimethyl chitosan, and polyethyleneimine-on the properties of the nanocrystals prepared by high-pressure homogenization method was investigated. Physicochemical properties of the nanoparticles were characterized. It was demonstrated that the cationic polymers could act as both an electrostatic and steric stabilizer to facilitate particle size reduction. Factors influencing charge density and stretching state of the cationic polymers influenced the magnitude of the particle. The electrostatic stabilization effect is more prominent than that of the steric stabilizing mechanism. Drug crystalline state was not changed by the addition of cationic polymers. Physical stability of the nanocrystals with cationic polymers was remarkably improved. The in vivo antifungal efficacy of the nanocrystals was dependent on physicochemical properties and pH. FROM THE CLINICAL EDITOR: Cationic polymer stabilizers were used to modify the surface of nanocrystals and the resulting stabilizing mechanisms were compared. The electrostatic stabilization effect was found to be stronger than the steric one. Crystallinity of itraconazole was unchanged by the addition of cationic polymers, while drug physical stability remarkably improved.

Deep purification of copper from Cu(II)-EDTA acidic wastewater by Fe(III) replacement/diethyldithiocarbamate precipitation.

Cu(II)-EDTA is a highly stable typical metal-organic complex in a wide pH range (3.0-12.0) and it is difficult to deeply purify Cu(II) by conventional precipitation methods. In this study, Fe(III) replacement/diethyldithiocarbamate (DDTC) precipitation combined process is proposed as a promising strategy to achieve the deep purification of Cu(II) from Cu(II)-EDTA acidic wastewater. The underlying mechanism has also been systematically elucidated by chemical equilibriums, experiments, and density functional theory (DFT) calculations, laying a foundation for the development and application. Chemical equilibriums show that Fe(III) replacement favors the stoichiometric release of Cu(II) from Cu(II)-EDTA and the formation of Fe(III)-EDTA complex under acidic conditions. Experimentally, Cu(II) is removed (over 99.99%) and deeply purified (under 0.008 mg/L) under the optimal conditions, which is lower than the most stringent discharge standards of copper ions in electroplating effluent (<0.5 mg/L, China). DFT calculations reveal that DDTC could further precipitate the released free copper ions via the carbon disulfide (-C(=S)-S) chelating group while exhibiting a slight effect on the Fe(III) in Fe(III)-EDTA. Considering these results, the electronic structures of Cu(II) and Fe(III), as well as their interaction with EDTA and DDTC ligands, are discussed to understand the mechanism of Fe(III)/DDTC process. By introducing a low dosage of Fe(III), the DDTC could efficiently purify Cu(II) from the Cu(II)-EDTA acid wastewater and realize the near-zero discharge of metal pollutants in metal-organic complex wastewater. It is believed that the main findings may benefit the water pollution reduction and comprehensive recycling of metal resources.

Complete genome sequence of the bacterium Ketogulonicigenium vulgare Y25.

Ketogulonicigenium vulgare is characterized by the efficient production of 2KGA from L-sorbose. Ketogulonicigenium vulgare Y25 is known as a 2-keto-L-gulonic acid-producing strain in the vitamin C industry. Here we report the finished, annotated genome sequence of Ketogulonicigenium vulgare Y25.

Mutation screening of HSF4 in 150 age-related cataract patients.

PURPOSE: Heat shock transcription factor 4 (HSF4) regulates the expression of several heat shock protein (HSP) genes. HSPs are one of the major components responsible for lens protein organization. Recently, we found that mutations of HSF4 result in hereditary cataract. In this study, we explore the role of HSF4 in the development of age-related cataract. METHODS: We screened sequence variants of HSF4 in age-related cataract patients and the natural population from Shanghai, China. RESULTS: In individuals of natural populations, we detected no single nucleotide polymorphism (SNP) with a frequency higher than 5% in a complete coding region or in their exon-intron boundaries. In 150 age-related cataract patients, we identified seven sequence changes. We found an intronic G-->A transition (c.1020-25G>A) in one patient, a missense mutation (c.1078A>G) in exon 4 in two patients, a silent mutation (c.1223 C>T) in exon 5 in two patients, an intronic C-->T transition (c.1256+25C>T) in one patient, and a silent mutation in exon 6 (c.1286 C>T) in one patient. These five variants were not represented in 220 control individuals. We also identified an intronic C-->T transition (c.1019+9C>T) and a missense mutation (c.1243G>A) in exon 3 in three patients, but these two variants were also present in 100 control subjects. CONCLUSIONS: We identified five new HSF4 mutations in 150 age-related cataract patients, enlarging the spectrum of HSF4 mutations in cataract patients. This result indicates that HSF4 mutations account for only a small fraction of age-related cataracts.

[Injury characteristics and therapeutic strategy of patients injured in "8·8" Jiuzhaigou earthquake].

Objective: To summarize the injury characteristics and therapeutic strategy of patients injured in "8·8" Jiuzhaigou earthquake. Methods: The clinical data of 48 patients injured in "8·8" Jiuzhaigou earthquake who were admitted to Mianyang Central Hospital were analyzed retrospectively. There were 25 males and 23 females with an average age of 36 years (range, 5-87 years). The average interval from injury to admission was 30 hours (range, 3-53 hours). The patients from Sichuan province accounted for 45.8% (22 cases), from other province for 52.1% (25 cases), and from abroad for 2.1% (1 case). Patients were primarily hurted by collapsing houses and flying stones. Thirty-seven patients (77.1%) had single injury, mainly involving 36 patients (75.0%) in limbs, and the other 11 patients (22.9%) had multiple injuries. Ten patients (20.8%) had open fractures, including 1 case rated as typeⅠ, 2 as typeⅡ, 3 as type Ⅲa, 2 as type Ⅲb, and 2 as type Ⅲc according to Gustilo classification criteria. The abbreviated injury scale (AIS) score was 2-3 in 37 patients of single injury, and the injury severity score (ISS) was 8-22 (mean, 13.2) in 11 patients of multiple injuries. Sixteen patients (33.3%) were diagnosed as mental disorders by Hamilton rating scale for anxiety (HAMA), including 8 cases had their anxiety scores≥29, 4 cases of 21-28, 3 cases of 14-20, and 1 case of 7-13. Of the 16 patients, 2 showed suicidal tendency. Results: Except 2 referrals, 30 patients received operationï¼»28 patients (93.3%) for orthopaedic surgeriesï¼½and 16 patients received conservative treatment. The procedures included internal fixation, soft tissue debridement, external fixation, bipolar femoral head replacement, embolization of carotid cavernous sinus arteriovenous fistula, and amputation. Among the 46 patients treated in this hospital, 21 discharged from hospital at 2-12 days (mean, 6.7 days) after admission, the others received further rehabilitation in this hospital or local hospital. No undesirable consequence occurred in 16 patients with mental disorders. Five cases of infection occurred out of hospital were cured after debridement. No dead and nosocomial infection case reported. Conclusion: Intensive treatment, specialist management, multidisciplinary team, and early intervention of nosocomial infection and deep venous thrombosis are the key to improve the general level of successful earthquake medical rescue.

Identification and classification of all potential hemolysin encoding genes and their products from Leptospira interrogans serogroup Icterohae-morrhagiae serovar Lai.

AIM: To identify and classify all potential hemolysin candidates of Leptospira interrogans serogroup Icterohaemorrhagiae serovar Lai. METHODS: All of the potential hemolysin encoding genes were characterized in silico. These genes were cloned and expressed in Escherichia coli. The hemolytic activities of the expressed proteins were assayed observing the hemolysis on sheep blood agar plates. Sphingomyelinase activities of the hemolysin candidates were measured by thin-layer chromatography (TLC) and HPLC for sphingomyelin-hydrolysis. Expression and secretion of the hemolysins in L interrogans were studied by reverse transcription polymerase chain reaction, Western blot, and enzyme-linked immunosorbent assays. RESULTS AND CONCLUSION: The hemolytic activities of hemolysin candidates (LA0327, LA0378, LA1027, LA1029, LA1650, LA3050, LA3937, LA4004) from L interrogans strain Lai were confirmed. They were further divided into two groups, sphingomyelinase hemolysins and non-sphingomyelinase hemolysins, based on their ability to hydrolyze sphingomyelin. Most of these hemolysins were actually expressed in living L interrogans and some of them were secreted into the environment. This study establishes an essential and complete basis for further studying the contribution of hemolysins to the pathogenesis of L interrogans.

Streptomyces akiyoshiensis differs from other gram-positive bacteria in the organization of a core biosynthetic pathway gene for aspartate family amino acids.

A partial Sau3Al digest of genomic DNA from Streptomyces akiyoshiensis was cloned in a Streptomyces-Escherichia coli shuttle vector, and the recombinant plasmids were used to transform E. coli CGSC 6212, which carries a mutation in the gene for aspartate semialdehyde dehydrogenase (Asd). One of 39,000 transformants tested grew on LB medium lacking diaminopimelate. A 17 kb plasmid (pJV21) isolated from this strain conferred prototrophy when used to transform E. coli CGSC 6212. The gene responsible was located on a 2.2 kb DNA fragment by subcloning. Nucleotide sequencing and codon preference analysis of the subcloned insert and of the 3.3 kb insert in the Asd(-)-complementing plasmid pJV36 located three complete and two incomplete open reading frames (ORFs). One of these (ORF3), encoding a polypeptide of 338 amino acids (Mr 35484), was identified as the gene for Asd by comparing its sequence with database sequences of asd from other bacteria. The inability of pJV30, in which a segment of ORF3 had been deleted, to transform E. coli CGSC 6212 to prototrophy supported this assignment. Southern hybridization indicated that the sequenced region of the cloned DNA fragment represented a continuous segment of the S. akiyoshiensis chromosome. The deduced amino acid sequences of the ORFs adjacent to asd showed no similarity to sequences for aspartate kinase (Ask); also, transformation with plasmids containing asd and adjacent regions from the S. akiyoshiensis chromosome did not complement the ask mutant E. coli CGSC 5074. It is concluded that asd and ask in S. akiyoshiensis are not present in an operon, and thus are organized differently from these genes in the Gram-positive bacteria previously examined.