A universal model to predict yields of THMs and HAAs based on UV-Visible absorption spectra.

Differential absorption spectroscopy (DAS) quantifies changes in the UV-Visible absorbance of dissolved organic matter (DOM) caused by reactions of its chromophores. As a result of its precision and sensitvity, DAS serves as a powerful tool for characterizing the formation of disinfection by-products (DBPs) in generated in DOM chlorination reactions. However, the nonlinear relationship between the intensity of DAS and DBP concentrations as well as the need to develop site-specific fitting parameters limit its practical applications. This study investigated the physico-chemical nature of DAS of chlorinated DOM through experimental measurements and theoretical calculations. Results of this study provide molecular-level evidence that electrophilic substitution reactions involving DOM reactive sites result in the emergence of DAS feaures ascribed to the "fast" chromophores. The ring opening in the cyclic enones-like structures which can be present either in the original DOM or are generated as intermediates in its chlorination, leads to the emergence of DAS features associated with the "slow" chromophores and high yields of DBPs. The kinetic study of chlorination of real waters reveals a strong linear relationship (R2 > 0.91) between ln([DBP]) and the long-wavelength (λ > 325 nm) parameter of the DAS, notably (ln(-DA350)). This relationship varies among different water sources due to the differences in the heterogeneity of Band A3 whose maximum is near 350 nm. Band A3 is one of the Gaussian bands that comprise the overall UV-Visible spectrum of DOM. A new function (f(-DA350)) is proposed in this study to quantify DBP formation. This function, which is determined by the Band A3's area, allows establishing a universal linear relationship between f(-DA350) and ln([THMs]), as well as f(-DA350) and ln([HAAs]), across various water sources. The findings of this study will stimulate further development of spectroscopy-based DBP monitoring technology for monitoring and optimization of water disinfection processes.

Induced regeneration of articular cartilage - identification of a dormant regeneration program for a non-regenerative tissue.

A mouse organoid culture model was developed to regenerate articular cartilage by sequential treatment with BMP2 and BMP9 (or GDF2) that parallels induced joint regeneration at digit amputation wounds in vivo. BMP9-induced chondrogenesis was used to identify clonal cell lines for articular chondrocyte and hypertrophic chondrocyte progenitor cells from digit fibroblasts. A protocol that includes cell aggregation enhanced by BMP2 followed by BMP9-induced chondrogenesis resulted in the differentiation of organized layers of articular chondrocytes, similar to the organization of middle and deep zones of articular cartilage in situ, and retained a differentiated phenotype following transplantation. In addition, the differentiation of a non-chondrogenic connective tissue layer containing articular chondrocyte progenitor cells demonstrated that progenitor cell sequestration is coupled with articular cartilage differentiation at a clonal level. The studies identify a dormant endogenous regenerative program for a non-regenerative tissue in which fibroblast-derived progenitor cells can be induced to initiate morphogenetic and differentiative programs that include progenitor cell sequestration. The identification of dormant regenerative programs in non-regenerative tissues such as articular cartilage represents a novel strategy that integrates regeneration biology with regenerative medicine.

Characterizing photochemical production carboxyl content of dissolved organic matters using absorbance spectroscopy combined with FT-ICR MS.

Irradiation can significantly impact the structure, reactivity and environmental behavior of dissolved organic matter (DOM). The extent of these processes remains to be ascertained in more detail but the heterogeneity and site-specificity of DOM, and the lack of methods to characterize DOM at its environmentally-relevant concentrations make it a challenge. In this study, the differences of DOM response to photodegradation in four typical origins (i.e., surface water, sediment and intracellular and extracellular algal DOM) were tracked on the molecular-level using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS). Changes of the carboxyl and phenolic DOM moieties induced by irradiation were quantified by spectroscopic titrations, and the mechanism of functional groups affecting the changes of specific molecular composition was qualitatively proposed. The results demonstrated that intracellular algal organic matter (I-DOM) was most susceptible to photodegradation (ca. 63% DOM loss), then came extracellular algal organic matter (E-DOM) and surface water DOM (W-DOM) (ca. 15% DOM loss). Sediment DOM (S-DOM) was most resistant to irradiation, with a very small level of its mineralization. Lipids, lignin-like compounds and tannin-like compounds in I-DOM and E-DOM were relatively photo-labile. The photodegradation of lipids was related to the decarboxylation of carboxyl functional groups, while the photodegradation of tannin-like compounds was related to the rupture of phenolic functional groups. In comparison, the molecular composition of W-DOM and S-DOM was less affected by irradiation, which was also reflected in the fact that the carboxyl and phenolic functional groups were highly photo-resistant. This study showed that the photoactivity of DOM in surface water was closely related to the abundance of algae, so controlling the excessive reproduction of algae may have a positive effect on stability of quality and quantity of organic matter in surface water.

Interpreting pH-Dependent Differential UV/VIS Absorbance Spectra to Characterize Carboxylic and Phenolic Chromophores in Natural Organic Matter.

Natural organic matter (NOM) is critical for the biogeochemical cycles of energy and many elements in terrestrial and aquatic ecosystems, and protonation-active functional groups in NOM molecules, notably carboxylic and phenolic groups often mediate these critical environmental functions. Molecular heterogeneity, polydispersity and dynamic behavior of NOM complicate achieving an unambiguous description of its molecular properties and reactivity. This study demonstrates that differential ultraviolet-visible (UV/VIS) absorbance spectra (DAS) of NOM acquired at varying pH values exhibit several distinct features associated with the deprotonation of NOM molecules, independent of the environmental provenance of NOM (e.g., surface water, seawater, sediment, and wastewater). The protonation-active functionalities that contribute to the Gaussian distribution bands present in the DAS were identified here by comparing characteristic properties of the bands with the stoichiometries of NOM molecules ascertained by Ultrahigh-Resolution Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS). The protonation-active individual chromophores universally present in NOM molecules were identified by a genetic molecular network analysis. The observed DAS features were closely modeled via superimposing DAS spectra of 51 individual protonation-active chromophores. Molecular orbital theory was applied to further interpret the deprotonation of these chromophores, their molecular structure, electron distribution, and electron transitions measured using DAS. The high sensitivity and easy implementation of the DAS approach allows using it as a powerful tool to quantify the molecular properties and reactivity of NOM at environmental concentrations.

A systematic review of predictive models for hospital-acquired pressure injury using machine learning.

AIMS AND OBJECTIVES: To summarize the use of machine learning (ML) for hospital-acquired pressure injury (HAPI) prediction and to systematically assess the performance and construction process of ML models to provide references for establishing high-quality ML predictive models. BACKGROUND: As an adverse event, HAPI seriously affects patient prognosis and quality of life, and causes unnecessary medical investment. At present, the performance of various scales used to predict HAPIs is still unsatisfactory. As a new statistical tool, ML has been applied to predict HAPIs. However, its performance has varied in different studies; moreover, some deficiencies in the model construction process were observed in each study. DESIGN: Systematic review. METHODS: Relevant articles published between 2010-2021 were identified in the PubMed, Web of Science, Scopus, Embase and CINHAL databases. Study selection was performed in accordance with the preferred reporting items for systematic reviews and meta-analysis guidelines. The quality of the included articles was assessed using the prediction model risk of bias assessment tool. RESULTS: Twenty-three studies out of 1793 articles were considered in this systematic review. The sample size of each study ranged from 149-75353; the prevalence of pressure injuries ranged from 0.5%-49.8%. ML showed good performance for HAPI prediction. However, some deficiencies were observed in terms of data management, data pre-processing and model validation. CONCLUSIONS: ML, as a powerful decision-making assistance tool, is helpful for the prediction of HAPIs. However, existing studies have been insufficient in terms of data management, data pre-processing and model validation. Future studies should address these issues to establish ML models for HAPI prediction that can be widely used in clinical practice. RELEVANCE TO CLINICAL PRACTICE: This review highlights that ML is helpful in predicting HAPI; however, in the process of data management, data pre-processing and model validation, some deficiencies still need to be addressed. The ultimate goal of integrating ML into HAPI prediction is to develop a practical clinical decision-making tool. A complete and rigorous model construction process should be followed in future studies to develop high-quality ML models that can be applied in clinical practice.

Microcomputed tomography staging of bone histolysis in the regenerating mouse digit.

Humans and mice have the ability to regenerate the distal digit tip, the terminal phalanx (P3) in response to amputation. What distinguishes P3 regeneration from regenerative failure is formation of the blastema, a proliferative structure that undergoes morphogenesis to regenerate the amputated tissues. P3 regeneration is characterised by the phases of inflammation, tissue histolysis and expansive bone degradation with simultaneous blastema formation, wound closure and finally blastemal differentiation to restore the amputated structures. While each regenerating digit faithfully progresses through all phases of regeneration, phase progression has traditionally been delineated by time, that is, days postamputation (DPA), yet there is widespread variability in the timing of the individual phases. To diminish variability between digits during tissue histolysis and blastema formation, we have established an in-vivo method using microcomputed tomography (micro CT) scanning to identify five distinct stages of the early regeneration response based on anatomical changes of the digit stump. We report that categorising the initial phases of digit regeneration by stage rather than time greatly diminishes the variability between digits with respect to changes in bone volume and length. Also, stages correlate with the levels of cell proliferation, osteoclast recruitment and osteoprogenitor cell recruitment. Importantly, micro CT staging provides a means to estimate open versus closed digit wounds. We demonstrate two spatially distinct and stage specific bone repair/regeneration responses that occur during P3 regeneration. Collectively, these studies showcase the utility of micro CT imaging to infer the composition of radiolucent soft tissues during P3 blastema formation. Specifically, the staging system identifies the onset of cell proliferation, osteoclastogenesis, osteoprogenitor recruitment, the spatial initiation of de novo bone formation and epidermal closure.

Deficiency and excess of groundwater iodine and their health associations.

More than two billion people worldwide have suffered thyroid disorders from either iodine deficiency or excess. By creating the national map of groundwater iodine throughout China, we reveal the spatial responses of diverse health risks to iodine in continental groundwater. Greater non-carcinogenic risks relevant to lower iodine more likely occur in the areas of higher altitude, while those associated with high groundwater iodine are concentrated in the areas suffered from transgressions enhanced by land over-use and intensive anthropogenic overexploitation. The potential roles of groundwater iodine species are also explored: iodide might be associated with subclinical hypothyroidism particularly in higher iodine regions, whereas iodate impacts on thyroid risks in presence of universal salt iodization exhibit high uncertainties in lower iodine regions. This implies that accurate iodine supply depending on spatial heterogeneity and dietary iodine structure optimization are highly needed to mitigate thyroid risks in iodine-deficient and -excess areas globally.

Digit specific denervation does not inhibit mouse digit tip regeneration.

It is long-established that innervation-dependent production of neurotrophic factors is required for blastema formation and epimorphic regeneration of appendages in fish and amphibians. The regenerating mouse digit tip and the human fingertip are mammalian models for epimorphic regeneration, and limb denervation in mice inhibits this response. A complicating issue of limb denervation studies in terrestrial vertebrates is that the experimental models also cause severe paralysis therefore impairing appendage use and diminishing mechanical loading of the denervated tissues. Thus, it is unclear whether the limb denervation impairs regeneration via loss of neurotrophic signaling or loss of mechanical load, or both. Herein, we developed a novel surgical procedure in which individual digits were specifically denervated without impairing ambulation and mechanical loading. We demonstrate that digit specific denervation does not inhibit but attenuates digit tip regeneration, in part due to a delay in wound healing. However, treating denervated digits with a wound dressing that enhances closure results in a partial rescue of the regeneration response. Contrary to the current understanding of mammalian epimorphic regeneration, these studies demonstrate that mouse digit tip regeneration is not peripheral nerve dependent, an observation that should inform continued mammalian regenerative medicine approaches.

Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides.

Transformation of metastable Fe(III) oxyhydroxides is a prominent process in natural environments and can be significantly accelerated by the coexisting aqueous Fe(II) (Fe(II)aq). Recent evidence points to the solution mass transfer of labile Fe(III) (Fe(III)labile) as the primary intermediate species of general importance. However, a mechanistic aspect that remains unclear is the dependence of phase outcomes on the identity of the metastable Fe(III) oxyhydroxide precursor. Here, we compared the coupled evolution of Fe(II) species, solid phases, and Fe(III)labile throughout the Fe(II)-catalyzed transformation of lepidocrocite (Lp) versus ferrihydrite (Fh) at equal Fe(III) mass loadings with 0.2-1.0 mM Fe(II)aq at pH = 7.0. Similar to Fh, the conversion of Lp to product phases occurs by a dissolution-reprecipitation mechanism mediated by Fe(III)labile that seeds the nucleation of products. Though for Fh we observed a transformation to goethite (Gt), accompanied by the transient emergence and decline of Lp, for initial Lp we observed magnetite (Mt) as the main product. A linear correlation between the formation rate of Mt and the effective supersaturation in terms of Fe(III)labile concentration shows that Fe(II)-induced transformation of Lp into Mt is governed by the classical nucleation theory. When Lp is replaced by equimolar Gt, Mt formation is suppressed by opening a lower barrier pathway to Gt by heterogeneous nucleation and growth on the added Gt seeds. The collective findings add to the mechanistic understanding of factors governing phase selections that impact iron bioavailability, system redox potential, and the fate and transport of coupled elements.

Epimorphic regeneration of the mouse digit tip is finite.

BACKGROUND: Structural regeneration of amputated appendages by blastema-mediated, epimorphic regeneration is a process whose mechanisms are beginning to be employed for inducing regeneration. While epimorphic regeneration is classically studied in non-amniote vertebrates such as salamanders, mammals also possess a limited ability for epimorphic regeneration, best exemplified by the regeneration of the distal mouse digit tip. A fundamental, but still unresolved question is whether epimorphic regeneration and blastema formation is exhaustible, similar to the finite limits of stem-cell mediated tissue regeneration. METHODS: In this study, distal mouse digits were amputated, allowed to regenerate and then repeatedly amputated. To quantify the extent and patterning of the regenerated digit, the digit bone as the most prominent regenerating element in the mouse digit was followed by in vivo µCT. RESULTS: Analyses revealed that digit regeneration is indeed progressively attenuated, beginning after the second regeneration cycle, but that the pattern is faithfully restored until the end of the fourth regeneration cycle. Surprisingly, when unamputated digits in the vicinity of repeatedly amputated digits were themselves amputated, these new amputations also exhibited a similarly attenuated regeneration response, suggesting a systemic component to the amputation injury response. CONCLUSIONS: In sum, these data suggest that epimorphic regeneration in mammals is finite and due to the exhaustion of the proliferation and differentiation capacity of the blastema cell source.

Hyaline cartilage differentiation of fibroblasts in regeneration and regenerative medicine.

Amputation injuries in mammals are typically non-regenerative; however, joint regeneration is stimulated by BMP9 treatment, indicating the presence of latent articular chondrocyte progenitor cells. BMP9 induces a battery of chondrogenic genes in vivo, and a similar response is observed in cultures of amputation wound cells. Extended cultures of BMP9-treated cells results in differentiation of hyaline cartilage, and single cell RNAseq analysis identified wound fibroblasts as BMP9 responsive. This culture model was used to identify a BMP9-responsive adult fibroblast cell line and a culture strategy was developed to engineer hyaline cartilage for engraftment into an acutely damaged joint. Transplanted hyaline cartilage survived engraftment and maintained a hyaline cartilage phenotype, but did not form mature articular cartilage. In addition, individual hypertrophic chondrocytes were identified in some samples, indicating that the acute joint injury site can promote osteogenic progression of engrafted hyaline cartilage. The findings identify fibroblasts as a cell source for engineering articular cartilage and establish a novel experimental strategy that bridges the gap between regeneration biology and regenerative medicine.

Mouse Digit Tip Regeneration Is Mechanical Load Dependent.

Amputation of the mouse digit tip results in blastema-mediated regeneration. In this model, new bone regenerates de novo to lengthen the amputated stump bone, resulting in a functional replacement of the terminal phalangeal element along with associated non-skeletal tissues. Physiological examples of bone repair, such as distraction osteogenesis and fracture repair, are well known to require mechanical loading. However, the role of mechanical loading during mammalian digit tip regeneration is unknown. In this study, we demonstrate that reducing mechanical loading inhibits blastema formation by attenuating bone resorption and wound closure, resulting in the complete inhibition of digit regeneration. Mechanical unloading effects on wound healing and regeneration are completely reversible when mechanical loading is restored. Mechanical unloading after blastema formation results in a reduced rate of de novo bone formation, demonstrating mechanical load dependence of the bone regenerative response. Moreover, enhancing the wound-healing response of mechanically unloaded digits with the cyanoacrylate tissue adhesive Dermabond improves wound closure and partially rescues digit tip regeneration. Taken together, these results demonstrate that mammalian digit tip regeneration is mechanical load-dependent. Given that human fingertip regeneration shares many characteristics with the mouse digit tip, these results identify mechanical load as a previously unappreciated requirement for de novo bone regeneration in humans. © 2021 American Society for Bone and Mineral Research (ASBMR).

Interpretation of the differential UV-visible absorbance spectra of metal-NOM complexes based on the quantum chemical simulations for the model compound esculetin.

In this study, the model compound esculetin that has functional groups typical for natural organic matter (NOM) was used to ascertain the nature of the characteristic bands in the differential UV-visible absorbance spectra (DAS) associated with the formation of metal-NOM complexes. The binding of ten different metal ions (Cu(II), Ni(II), Co(II), Fe(III), Cr(III), Al(III), Zn(II), Ca(II), Mg(II) and Pb(II)) with esculetin generate four bands in the DAS. These bands are similar to those present in the DAS of metal-NOM complexes. The UV-visible absorbance spectra of the metal-esculetin systems were calculated using time-dependent density functional theory (TD-DFT). The TD-DFT results demonstrate that the prominent features of the DAS of esculetin are primarily associated with the electron transitions between the molecular orbitals near the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in the metal-esculetin complex. Charge decomposition analysis (CDA) results demonstrated that these electron transitions originate from the esculetin fragment to the Zn(II) fragment in the complex. Covalent indexes [(χm)2rc] of the metal ions were found to be correlated with the metal-specific features of the DAS of metal-esculetin systems. The strength of the linear correlations between the quantitative parameters of the electron density of the bond critical points (BCP) is indicative of the strength of the metal-esculetin interactions.

Interpretation of the formation of unstable halogen-containing disinfection by-products based on the differential absorbance spectroscopy approach.

Concentrations of several toxic disinfection by-products (DBP), notably haloacetonitriles (e.g., trichloroacetonitrile, TCAN) and haloketones (e.g., di- and trichloropropanone, DCPN and TCPN, respectively) are affected by chlorination conditions and the inherent instability of these DBPs. In this study, effects of temperature, chlorine dose and reaction time on the formation of TCAN, DCPN and TCPN were interpreted using the approach of differential absorbance spectroscopy. Experimental data obtained for a wide range of water quality conditions demonstrate that in some cases the concentrations of some of the unstable DBPs increased rather than decreased at low temperatures and realistically long contact times. Despite the presence of pronounced changes of the kinetics of generation and degradation of these DBPs at varying temperatures and chlorine doses, their concentrations were strongly correlated with the concurrent changes of spectroscopic properties of DOM quantified via differential absorbance measurements at 272 nm (ΔA272). The maximum values of TCAN, DCPN and TCPN concentrations observed for the chlorination of eight different surface waters occur at the relative decreases of absorbance at 272 nm (defined as RΔA272) values of ca. 0.32 (±0.03), 0.24 (±0.05), and 0.42 (±0.03), respectively. The activation energies of degradation reactions of unstable DBPs were examined and the results indicate that TCAN and TCPN are caused by their hydrolysis with OH- while the degradation of DCPN is mainly caused by halogenation reaction with HOCl. These results in this study may be important for controlling the formation of unstable DBPs and further optimization of drinking water treatment.

Effects of pre-oxidation on residual dissolved aluminum in coagulated water: A pilot-scale study.

Residual dissolved aluminum (Al) in drinking water is becoming a serious concern due to its high potential risks to human health. However, the mechanism by which residual dissolved Al forms is yet to be elucidated in detail. In this study, the effects of pre-oxidation by ozonation and chlorination on the properties of dissolved organic matter (DOM) and residual Al concentrations remaining in solution after coagulation were explored in a pilot-scale test. Changes in the DOM properties caused by the water treatment process were characterized by ultraviolet-visible absorbance spectroscopy. Theprotonation-active sites, carboxylic- and phenolic-type groupsof DOM were quantified by spectral parameter DlnA400 (differential log-transformed spectra at wavelength 400 nm) in combination with the revised non-ideal competitive adsorption model. The results show that ozonation and chlorination significantly affect the properties of DOM and the amount of residual dissolved Al in coagulated drinking water. This effect was associated with the changes in the carboxylic- and phenolic-type groups in DOM. Results of the study show that residual dissolved Al in coagulated water can be controlled by affecting theAl binding sites in DOM by pre-oxidation before coagulation. The nature of pre-oxidation agent and its dosage should be selected depending on the quality of the raw water to be treated. Ozonation was concluded to be preferable pre-oxidation agent for the water in examined this study.

Competition between Al(III) and Fe(III) for binding onto natural organic matter: In situ monitoring by UV-Vis absorbance spectroscopy.

The ubiquitous presence of natural organic matter (NOM) in the aquatic and soil environment significantly affects the transport, fate and bioavailability of Al and Fe elements, NOM itself and other trace metals. In this study, the binding of Al(III) and Fe(III) and their competition for binding onto NOM at varying pH values were monitored in situ via UV-Vis absorbance spectroscopy. It demonstrated that the spectral parameter, e.g., the differential log-transformed absorbance at 400 nm (ΔLnA400), can quantify the amount of Al(III) and/or Fe(III) bound onto NOM in all examined cases and will show similar molar extinction coefficients that correspond to the amount of bound Al(III) and Fe(III). Therefore, this approach can not only demonstrate visibly the competition between Al(III) and Fe(III) based on their metal-specific features by evaluating differential absorbance spectra produced by metal binding but can also monitor the reaction kinetics of Al(III) and Fe(III) and their competition for binding onto NOM. To our knowledge, this study is the first to in situ monitor the competition between Al(III) and Fe(III) for binding with NOM quantitatively and at realistic environmental concentrations of both metal ions and NOM.

Proximal digit tip amputation initiates simultaneous blastema and transient fibrosis formation and results in partial regeneration.

Complete extremity regeneration in mammals is restricted to distal amputations of the digit tip, the terminal phalanx (P3). In mice, P3 regeneration is mediated via the formation of a blastema, a transient population of progenitor cells that form from the blending of periosteal and endosteal/marrow compartmentalized cells that undergo differentiation to restore the amputated structures. Compartmentalized blastema cells are formed independently, and periosteal compartment-derived cells are required for restoration of amputated skeletal length. P3 regenerative capacity is progressively attenuated at increasingly more proximal amputation levels, eventually resulting in regenerative failure. The continuum of regenerative capacity within the P3 wound milieu is a unique model to investigate mammalian blastema formation in response to distal amputation, as well as the healing response associated with regenerative failure at proximal amputation levels. We report that P3 proximal amputation healing, previously reported to result in regenerative failure, is not an example of complete regenerative failure, but instead is characterized by a limited bone regeneration response restricted to the endosteal/marrow compartment. The regeneration response is mediated by blastema formation within the endosteal/marrow compartment, and blastemal osteogenesis progresses through intramembranous ossification in a polarized proximal to distal sequence. Unlike bone regeneration following distal P3 amputation, osteogenesis within the periosteal compartment is not observed in response to proximal P3 amputation. We provide evidence that proximal P3 amputation initiates the formation of fibrotic tissue that isolates the endosteal/marrow compartment from the periosteal compartment and wound epidermis. While the fibrotic response is transient and later resolved, these studies demonstrate that blastema formation and fibrosis can occur in close proximity, with the regenerative response dominating the final outcome. Moreover, the results suggest that the attenuated proximal P3 regeneration response is associated with the absence of periosteal-compartment participation in blastema formation and bone regeneration.

Interpreting main features of the differential absorbance spectra of chlorinated natural organic matter: Comparison of the experimental and theoretical spectra of model compounds.

This study compared chlorination-induced changes of the properties of natural organic matter (NOM) represented by standard humic substances and NOM present in pristine and anthropogenically-affect reservoirs, rivers, groundwater and seawater. The chlorination-induced changes of NOM properties were quantified using the differential absorbance spectra (DAS) which were processed via numeric deconvolution. Six Gaussian bands were found to comprise the DAS of all examined waters. These bands (denoted as A0, A1, A2, A3, A4 and A5, respectively) have maxima located at ca. 200, 240, 276, 316, 385 and 547 nm. The bands A1-A4 were observed in the DAS of representative model chlorinated compounds. Quantum chemical (QC) calculations were carried out to examine the intrinsic nature of these bands and electronic transitions associated with them. QC data demonstrate that bands A1 and A2 are present in almost all aromatic organic species, A3 is likely to be associated with acetophenone- and/or styrene-like groups. A4 can be attributed to the engagement of m-hydroxyaromatic and flavone-type groups typical for the polyphenolic moiety in NOM and known to be the key precursors of disinfection by-product (DBP) formation. Thus, the intensity of band A4 is predicted to be an especially strong predictor of DBP formation.

Recovery of phosphorus and metallic nickel along with HCl production from electroless nickel plating effluents: The key role of three-compartment photoelectrocatalytic cell system.

A three-compartment photoelectrocatalytic (PEC) cell system combined with ion exchange and chemical precipitation was proposed to recover phosphorus and nickel from electroless nickel plating effluents containing hypophosphite (H2PO2-) and nickel ions (Ni2+). Ion exchange was used to concentrate and separate Ni2+ and H2PO2-. As a key unit, the established PEC system consisted of TiO2/Ni-Sb-SnO2 photoanode and Ti cathode. With 25.8 mM NaH2PO2 and 500 mM NiCl2, 100 % H2PO2- was oxidized to PO43- in the anode cell, 78 % Ni2+ was recovered as metallic Ni in the cathode cell, and 900 mM HCl was obtained in the middle cell within 24 h at 3.0 V. Based on quenching experiments and ESR technique, OH radicals were mainly responsible for H2PO2- oxidation. In situ Raman spectroscopy indicated that Ni2+ initially reacted with OH- to form α-Ni(OH)2, which was gradually reduced to metallic Ni. Fortunately, a slight pH decrease in the cathode cell in the three-compartment cell system was beneficial for Ni2+ reduction to Ni°. The obtained PO43- was recovered by chemical precipitation. Finally, recovery of phosphorus and metallic nickel along with HCl production from an actual electroless nickel plating effluents in terms of efficiency, cost-benefit, and stability assessment were demonstrated.

Investigation of the deprotonation of tetracycline using differential absorbance spectra: A comparative experimental and DFT/TD-DFT study.

Tetracycline is a type of broad-spectrum, naturally occurring antibiotic that leads to several side effects, such as affecting intestinal flora and increase in bacterial resistance. The affinity of tetracycline for abiotic and biotic surfaces and metal ions is closely related to its deprotonation state and charge distribution; however, its deprotonation-protonation property remains unclear. In this study, the hydrolysis of tetracycline was investigated by combining experiments with quantum-chemical calculations. The molecular structure of the probable deprotonation states were optimized by quantum-chemical calculations, and the corresponding absorbance spectra were predicted based on frontier molecular orbital (FMO) theory. The absorbance spectra showed structure-specific features at the different deprotonation states. In addition, changes in tetracycline absorbance spectra in the pH range of 2.00-12.00 was examined by spectroscopic titration. The deprotonation was found to proceed in the order of site 3, 4, 12, and 10, which was identified by comparing the quantum-chemical calculations and experimental differential absorbance spectra (DAS). The results in this study are of great significance for further studies of the transport and fate of tetracycline in the environment.