Evaluation of Copper Levels in Dental Calculus of OSF Patients with Chewing Dried Areca-Nut Quids in Hunan Province of Mainland China.

Dental calculus is a potential material that can be used for assessing chronic exposure to trace heavy metals in oral cavity as it is a long-term reservoir. The aim of this study was to investigate the correlation between dental calculus copper levels and risk of oral submucous fibrosis (OSF) due to chewing dried areca-nut quids in Mainland China. This study included 34 OSF (grade 1) sufferers with dried areca-nut quids chewing as the patient group and 23 healthy individuals without areca-nut chewing as the control group. The dental calculus sample was obtained from all 57 participants and evaluated by inductively coupled plasma mass spectrometry (ICP-MS) for dental calculus level of copper. This work revealed that the mean copper level of dental calculus was significantly higher in OSF (grade 1) sufferers with areca-nut chewing than those in healthy individuals without areca-nut chewing (p < 0.001). This work provided an evidence to support that there may be a positive correlation between elevated levels of copper in dental calculus caused by chewing dried areca-nut quids and an increased risk of developing OSF in Mainland China.

Exploiting Wavelength Orthogonality in Photoinitiated RAFT Dispersion Polymerization and Photografting for Monodisperse Surface-Functional Polymeric Microspheres.

We report a strategy toward surface-functional polymeric microspheres using a wavelength orthogonality technique that employs photoinitiated reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization and the subsequent photografting under different wavelengths of light. Initial screening of reaction conditions indicated photoreactive polymeric microsphere with uniform sizes could be prepared by using photoinitiator-functionalized macro-RAFT agents under purple light irradiation. Photoreactive polymeric microspheres allowed photografting polymerizations under UV light irradiation, and we further demonstrated the broad scope of this method by photografting acrylamide, acrylic, and methacrylic monomers. Finally, carboxyl-functionalized polymeric microspheres with an exceptional high number of carboxyl groups were successfully prepared by this technique, which permitted extensive surface bioconjugation of model proteins (e.g., streptavidin). This method should expand the capabilities of RAFT dispersion polymerization to afford diverse surface-functional polymeric microspheres for some specific applications.

Hydrochloride fasudil attenuates brain injury in ICH rats.

AIM: The aim of this study was to investigate the neuroprotective effects of hydrochloride fasudil (HF) in rats following intracerebral hemorrhage (ICH). METHODS: Male Wistar rats were randomly divided into four groups: normal, sham-operated, ICH, and ICH/HF. ICH was induced by injection of non-anticoagulant autologous arterial blood into the right caudate nucleus. The levels of Rho-associated protein kinase 2 (ROCK2) mRNA and protein around the site of the hematoma were measured by quantitative real-time polymerase chain reaction and enzyme-linked immunosorbent assay (ELISA), respectively. The levels of interleukin-6 and tumor necrosis factor-α in serum were detected by ELISA. The inflammatory cells and changes in the neuronal morphology around the hematoma were visualized using hematoxylin and eosin and Nissl staining. Brain edema was measured by comparing wet and dry brain weights. RESULTS: Following ICH, the levels of ROCK2 were significantly increased from day 1 to day 7. The levels of ROCK2 were significantly lower in rats treated with HF than in controls. The levels of inflammatory cytokines and brain water content were significantly higher in rats treated with HF than in controls. Administration of HF significantly reduced the levels of inflammatory cytokines and brain water content from day 1 to day 7. In the acute phase of ICH, a large number of neutrophils infiltrated the perihematomal areas. In comparison with the ICH group, the ICH/HF group showed markedly fewer infiltrating neutrophils on day 1. Nissl staining showed that ICH caused neuronal death and loss of neurons in the perihematomal areas at all time points and that treatment with HF significantly attenuated neuronal loss. CONCLUSIONS: HF exerts neuroprotective effects in ICH rats by inhibiting the expression of ROCK2, reducing neutrophil infiltration and production of inflammatory cytokines, decreasing brain edema, and attenuating loss of neurons.

Evaluation of Cadmium Levels in Dental Calculus of Male Oral SCC Patients with Betel-Quid Chewing in Hunan Province of China.

Cadmium (Cd) is a widespread trace toxic heavy metal with long biological half-life and may induce higher risk of cancer on multiple organs of human body. Recent studies have confirmed that dental calculus has enormous potential for investigation of exposure to Cd in the human mouth by acting as a time capsule. We aimed to examine relationship between Cd levels in dental calculus due to betel-quid chewing and risk of oral cancer. This study included 85 male oral squamous cell carcinoma (SCC) cases with betel-quid chewing and smoking as observation subjects (group A) and 67 healthy people with smoking but without betel-quid chewing as control subjects (group B) in Hunan province of Mainland China. Cd levels in calcified dental calculus samples from all participants were measured by inductively coupled plasma mass spectrometry (ICP-MS). The results of this study indicated that cadmium levels in dental calculus were significantly higher in male oral SCC patients with betel-quid chewing and smoking than that in healthy individuals without habit of betel-quid chewing and with smoking (p < 0.0001). This study gives some evidence to support that there may be a positive relationship between cadmium in dental calculus due to betel-quid chewing and risk of oral SCC.

Mechanochemical pre-treatment for viable recycling of plastic waste containing haloorganics.

Chemical recycling technologies are the most promising for a waste-to-energy/material recovery of plastic waste. However, 30% of such waste cannot be treated in this way due to the presence of halogenated organic compounds, which are often utilized as flame retardants. In fact, high quantities of hydrogen halides and dioxin would form. In order to enabling such huge amount of plastic waste as viable feedstock for recycling, an investigation on mechanochemical pre-treatment by high energy ball milling is carried out on polypropylene containing decabromodiphenyl ether. Results demonstrate that co-milling with zero valent iron and quartz sand ensures complete debromination and mineralization of the flame retardant. Furthermore, a comparative experiment demonstrates that the mechanochemical debromination kinetics is roughly proportional to the polymer-to-haloorganics mass ratio.

Cadmium Profiles in Dental Calculus: a Cross-Sectional Population-Based Study in Hunan Province of China.

We aimed to investigate whether the cadmium concentrations differ in human dental calculus obtained from the residents with no smoking living in the contaminated area and those with no smoking living in noncontaminated area. In total, there were 260 samples of dental calculus from the adults (n = 50) with no smoking living in contaminated area, the adults (n = 60) with no smoking living in mountainous area, and the adults (n = 150) with no smoking living in low altitude area in Hunan province of China. All samples were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) for cadmium levels. The cadmium levels in dental calculus were significantly higher in the adults with no smoking living in contaminated area than those living in mountainous area and in low altitude area (p < 0.01). The cadmium levels in dental calculus were also higher in the adults with no smoking living in low altitude area than those living in mountainous region (p < 0.01). The results suggested that measuring cadmium levels in dental calculus may be a useful noninvasive method for analysis of environmental exposure to cadmium in the human oral cavity. The low altitude region may have an area contaminated with cadmium in Hunan province of China.

Mechanochemical mineralization of "very persistent" fluorocarbon surfactants ‒ 6:2 fluorotelomer sulfonate (6:2FTS) as an example.

Fluorinated organic chemicals have a wide variety of industrial and consumer applications. For long time perfluorooctane sulfonate and perfluorooctanoic acid have been used as precursors for manufacture of such chemicals. However, these C8 chain compounds have been demonstrated to be toxic, persistent, and bioaccumulative, thus inducing their phase-out. Currently, C6 telomer based fluorocarbon surfactants are considered better alternatives to C8 products because of their low bioaccumulability. But, their high persistency suggests that in the near future their concentrations will increase in the environment and in industrial waste. Being a solid state non-thermal technology, mechanochemical treatment is a good candidate for the destruction of emerging C6 fluorotelomers in solid waste. In the present study, 6:2 fluorotelomer sulfonate is effectively destroyed (~100%) in rapid manner (<1 h) by high energy ball milling with KOH. Stoichiometric fluoride formation confirms its entire mineralization, assuring that no toxic by-products are generated. Reaction mechanism and kinetics indicate that effective mineralization of the perfluorinated moiety is obtained thanks to a rapid CF2 "flake-off" process through radical mechanism.

Vehicles as outdoor BFR sources: Evidence from an investigation of BFR occurrence in road dust.

The distribution of brominated flame retardants (BFRs) including ∑8PBDEs, DBDPE, BTBPE, EH-TBB, BEH-TEBP and PBEB in road dust (RD) collected in Xinxiang, China was characterized. Analysis of RD samples indicated that the BFR abundance declined as traffic density decreased, with total mean levels of 292, 184, 163, 104 and 70 ng g-1 dust at sites from traffic intersections, main roads, collector streets, bypasses and parks, respectively. A possible explanation for this phenomenon is that the majority of BFRs may be emitted from the interior of vehicles via their ventilation systems. Of the 13 analyzed substances, BDE-209 and BEH-TEBP were the most abundant components in RD from Xinxiang. Similar amounts of ∑BDEs excluding BDE-209 were found at different types of sampling sites, and thus, atmospheric deposition is also a probable source of BFRs in RD which can be subject to air transportation. The main PBDE sources were traced to commercial products including DE-71, Bromkal 79-8DE, Saytex 201E and Bromkal 82 DE mixtures. Our results confirm that the use of deca-BDE commercial mixture is a major source of PBDE contamination in RD. Risk assessment indicated the concentrations of BFRs in RD in this study do not constitute a non-cancer or cancer risk to humans through ingestion. Annual emission fluxes of the commonly detected BFRs via RD in China were estimated to be up to 4980 kg year-1.

Mechanochemical remediation of PCB contaminated soil.

Soil contaminated by polychlorinated biphenyls (PCBs) is a ubiquitous problem in the world, which can cause significant risks to human health and the environment. Mechanochemical destruction (MCD) has been recognized as a promising technology for the destruction of persistent organic pollutants (POPs) and other organic molecules in both solid waste and contaminated soil. However, few studies have been published about the application of MCD technology for the remediation of PCB contaminated soil. In the present study, the feasibility of destroying PCBs in contaminated soil by co-grinding with and without additives in a planetary ball mill was investigated. After 4 h milling time, more than 96% of PCBs in contaminated soil samples were destroyed. The residual concentrations of PCBs decreased from 1000 mg/kg to below the provisional Basel Convention limit of less than 50 mg/kg. PCDD/F present in the original soil at levels of 4200 ng TEQ/kg was also destroyed with even a slightly higher destruction efficiency. Only minor dechlorinations of the PCBs were observed and the destruction of the hydrocarbon skeleton is proposed as the main degradation pathway of PCBs.

A study of cell proliferation using immunohistological staining: A case report of congenital granular cell epulis.

An unusual case of a 1-day-old Chinese female neonate with a solid tumor mass in the maxillary anterior ridge of the edentulous jaw is reported. Based on the clinical and histopathological features, the diagnosis was of obstructive congenital granular cell epulis (CGCE) which is an uncommon benign tumor that preferentially develops in female infants. Immunohistochemical analysis of the lesion was performed and the rate of cell proliferation was determined by immunostaining with Ki-67 and PCNA, which showed labeling indexes of 11.1% and 33.3%, respectively. No recurrence was observed in the follow-up.

Mechanochemical conversion of brominated POPs into useful oxybromides: a greener approach.

Brominated organic pollutants are considered of great concern for their adverse effect on human health and the environment, so an increasing number of such compounds are being classified as persistent organic pollutants (POPs). Mechanochemical destruction is a promising technology for POPs safe disposal because it can achieve their complete carbonization by solvent-free high energy ball milling at room temperature. However, a large amount of co-milling reagent usually is necessary, so a considerable volume of residue is produced. In the present study a different approach to POPs mechanochemical destruction is proposed. Employing stoichiometric quantities of Bi2O3 or La2O3 as co-milling reagent, brominated POPs are selectively and completely converted into their corresponding oxybromides (i.e. BiOBr and LaOBr), which possess very peculiar properties and can be used for some actual and many more potential applications. In this way, bromine is beneficially reused in the final product, while POPs carbon skeleton is safely destroyed to amorphous carbon. Moreover, mechanochemical destruction is employed in a greener and more sustainable manner.

Mechanochemical destruction of halogenated organic pollutants: A critical review.

Many tons of intentionally produced obsolete halogenated persistent organic pollutants (POPs), are stored worldwide in stockpiles, often in an unsafe manner. These are a serious threat to the environment and to human health due to their ability to migrate and accumulate in the biosphere. New technologies, alternatives to combustion, are required to destroy these substances, hopefully to their complete mineralization. In the last 20 years mechanochemical destruction has shown potential to achieve pollutant degradation, both of the pure substances and in contaminated soils. This capability has been tested for many halogenated pollutants, with various reagents, and under different milling conditions. In the present paper, a review of the published work in this field is followed by a critique of the state of the art of POPs mechanochemical destruction and its applicability to full-scale halogenated waste treatment.

Sodium persulfate-assisted mechanochemical degradation of tetrabromobisphenol A: Efficacy, products and pathway.

In recent years, activated persulfate (PS) oxidation has been developed as a new advanced oxidation process for the degradation of organic pollutants. On the other hand, the mechanochemical method has exhibited a unique advantage in dealing with chemical wastes. The degradation of tetrabromobisphenol A (TBBPA), a widely used brominated flame retardant (BFR), in wastes has attracted considerable attention. In this study, the efficacy of a CaO-mechanochemical (CaO-MC) treatment system assisted by the addition of PS for the degradation of TBBPA was investigated. Under the optimum reaction conditions with a mole ratio of PS:CaO = 1:4 and less than 12.5% of TBBPA by mass, the degradation and debromination of TBBPA were completed within 2 h, while the mineralization was completed within 4 h. Characterization of the milled sample by XRD revealed that CaSO4 crystallization occurred. The TG results illustrate that there was little organic matter left after 4 h of milling. Raman and FT-IR spectra exhibited the TBBPA destruction process and disappearance of the organic groups. Through analysis by LC/MS/MS, seventeen intermediates were identified. The mechanism of TBBPA degradation by the PS-assisted CaO-MC treatment system was explained from two aspects, the course of crystallization and the degradation of TBBPA by activated PS, and two parallel initiation pathways were proposed.

Ball milling synthesized MnOx as highly active catalyst for gaseous POPs removal: significance of mechanochemically induced oxygen vacancies.

A rapid (1.5 h) one-step ball milling (BM) method was developed not only to modify commercial MnO2 via top-down approaches (BM0), but also to bottom-up synthesize MnO(x) by cogrinding of KMnO4 and MnC4H6O4 (BM1) or KMnO4 and MnSO4 (BM2). Catalysts activity on gaseous POPs removal was tested using hexachlorobenzene (HCBz) as surrogate. Catalytic performance decreases in the order of BM2 ≈ BM1 (T90% = 180-200 °C) > BM0 (260 °C) > CMO ≈ cryptomelane MnO2 (>300 °C). Both adsorption and destruction contribute to HCBz removal at 180 °C while destruction prevails at 200-300 °C. Mechanism studies show that destruction activity is lineally correlated with the amount of surface reactive oxygen species (Oads); stability is determined by the removal of surface chloride, which is associated with the mobility of bulk lattice oxygen (Olat); adsorption capacities are linearly correlated with surface area and pore structure. With the aid of extensive characterizations the excellent performance of BM prepared samples can be explained as (1) abundant surface vacancies enhance the generation of Oads; (2) massive bulk vacancies promote the mobility of bulk Olat; (3) large surface area and uniform pore size distribution facilitate the physisorption of HCBz.

Mechanochemical degradation of hexabromocyclododecane and approaches for the remediation of its contaminated soil.

Hexabromocyclododecane (HBCD) has been listed in the Stockholm Convention for elimination due to its persistent and accumulative properties. In consideration of its sound disposal, mechanochemical (MC) method was employed using different co-milling reagents. Fe-Quartz was proven to a good reagent for HBCD destruction achieving both good degradation efficiency and high yield of bromide. The absence of organic matters after MC treatment was demonstrated by thermogravimetry and GC-MS analysis, indicating the complete degradation of HCBD and its conversion into inorganic compounds. No obvious intermediates could be detected due to the swift and spontaneous reaction between HBCD and Fe-Quartz. FTIR and Raman spectra further showed that the organic structures in HBCD were broken down while amorphous and graphite carbon were obtained as another final product besides bromide. After the successful destruction of HBCD, approaches to remediate its contaminated soil were also carried out. Fe-Quartz was also proven to be the best reagent for HBCD degradation in Kaolin, while CaO showed better performance for the remediation of HBCD contaminated Krasnozem. For practical application, preliminary experiments are necessary in order to select a suitable co-milling reagent and a proper milling time depending on the differences in soil properties and HBCD concentration.

Stability of 6:2 fluorotelomer sulfonate in advanced oxidation processes: degradation kinetics and pathway.

Perfluorooctane sulfonate (PFOS), a widely used mist suppressant in hard chrome electroplating industry, has been listed in the Stockholm Convention for global ban. 6:2 Fluorotelomer sulfonate (6:2 FTS) acid and salts have been adopted as alternative products in the market, but no data about their abiotic degradation has been reported. In the present study, the degradability of 6:2 FTS potassium salt (6:2 FTS-K) was evaluated under various advanced oxidation processes, including ultraviolet (UV) irradiation, UV with hydrogen peroxide (H2O2), alkaline ozonation (O3, pH = 11), peroxone (O3/H2O2), and Fenton reagent oxidation (Fe(2+)/H2O2). UV/H2O2 was found to be the most effective approach, where the degradation of 6:2 FTS-K followed the pseudo-first-order kinetics. The intermediates were mainly shorter chain perfluoroalkyl carboxylic acid (C7 to C2), while sulfate (SO4 (2-)) and fluoride (F(-)) were found to be the final products. The high yields of SO4 (2-) and F(-) indicate that 6:2 FTS-K can be nearly completely desulfonated and defluorinated under UV/H2O2 condition. The degradation should firstly begin with the substitution of hydrogen atom by hydroxyl radicals, followed by desulfonation, carboxylation, and sequential "flake off" of CF2 unit. Compared with PFOS which is inert in most advanced oxidation processes, 6:2 FTS-K is more degradable as the alternative.

Effects of zero-valent metals together with quartz sand on the mechanochemical destruction of dechlorane plus coground in a planetary ball mill.

Mechanochemical destruction by grinding with additives in high energy ball milling has been identified as a good alternative to traditional incineration for the disposal of wastes containing halogenated organic pollutants. Despite CaO normally used as an additive, recently Fe+SiO2 has been used to replace CaO for a faster destruction. In the present study, zero-valent metals (Al, Zn, besides Fe) together with SiO2 were investigated for their efficiencies of prompting the destruction of dechlorane plus (DP). Aluminum was found of be the best with a destruction percentage of nearly 99% for either syn- or anti-DP after 2.5h milling. In comparison, only 88/85% and 37/32% of syn-/anti-DP were destroyed when using zinc and iron after the same time, respectively. The detected water soluble chloride was lower than the stoichiometric amount containing in the original DP samples, due to the Si-Cl bond formed during the process. The potential fate of C and Cl present in DP is in the form of inorganic carbon, inorganic Cl and formation of Si-Cl bonds, respectively. The results suggested that Al+SiO2 is promising in the mechanochemical destruction of chlorinated organic pollutants like DP.

Destruction of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) by ball milling.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have received high concerns due to their extreme persistence, and very few technologies have been reported for their complete destruction. For sound PFCs wastes disposal, mechanochemical method was employed using a planetary ball mill. Potassium hydroxide (KOH) was identified as the best comilling reagent and nearly complete destruction of both PFOS and PFOA was realized. The measured water-soluble fluoride accounted for most of the organic fluorine. The final products of PFOS after treatment were shown to be KF and K2SO4 by XRD analysis. The mass ratio between PFOS and KOH significantly affected the fluoride recovery but not for PFOS destruction and the sulfate recovery. The gradual formation of sulfate and fluoride reveals that the degradation of PFOS is initiated with the dissociation of the sulfonate group. FTIR spectra further showed the disappearance of the -CF3 and -CF2- groups with the generation of sulfate. The cleavage of C-F bonds in PFOS and the formation of fluoride ion were also identified by XPS spectra. On the basis of these results, possible reaction pathways were proposed. The approach was also successfully applied for the destruction of PFOS and PFOA homologues with different chain lengths.

Mechanochemical destruction of mirex co-ground with iron and quartz in a planetary ball mill.

Mechanochemical destruction (MCD) has been recognized as a promising non-combustion technology for the disposal of obsolete pesticides belonging to the persistent organic pollutants (POPs). Mirex, a termiticide ever used for many years in China, was ball milled in the presence of various reagent(s) in a planetary ball mill at room temperature to investigate the destruction efficiency. The ground samples were characterized and analyzed by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, gas chromatography (GC), and ion chromatography (Martins, Bicego et al.). Under the same conditions of mill rotary rate and charge ratio, the mixture of iron powder and quartz sand (Fe/SiO(2)) was found best in promoting the mirex destruction. Mirex was completed destroyed after 2 h grinding at a charge ratio of 36:1 (reagent/mirex, m/m) and a mill rotation speed of 550 rpm. No organic compound was detected by GC/µECD screening. The yield of water-soluble chlorine determined by ion chromatography (Martins, Bicego et al.) in the final residue accounted for 90.7% of chlorine in the original mirex, which indicated a nearly complete dechlorination. Signals of both graphite and amorphous carbon were found in the Raman spectra of the co-ground powder samples. With the main final degradation products of water soluble Cl and carbon, the mechanism of the mechanochemical destruction approach should be dechlorination followed by the carbonization.