Diselenophosphate Ligands as a Surface Engineering Tool in PdH-Doped Silver Superatomic Nanoclusters.

The first hydride-doped Pd/Ag superatoms stabilized by selenolates are reported: [PdHAg19(dsep)12] [dsep = Se2P(OiPr)2] 1 and [PdHAg20(dsep)12]+ 2. 1 was derived from the targeted transformation of [PdHAg19(dtp)12] [dtp = S2P(OiPr)2] by ligand exchange, whereas 2 was obtained from the addition of trifluoroacetic acid to 1, resulting in a symmetric redistribution of the capping silver atoms. The transformations are all achieved while retaining an 8-electron superatomic configuration. VT-NMR attests to the good stability of the NCs in solution, and single-crystal X-ray diffraction reveals the crucial role that the interstitial hydride plays in directing the position of the capping silver atoms. The total structures are reported alongside their electronic and optical properties. 1 and 2 are phosphorescent with a lifetime of 73 and 84 µs at 77 K, respectively. The first antibacterial activity data for superatomic bimetallic Pd/Ag nanoclusters are also reported.

Controlled Shell and Kernel Modifications of Atomically Precise Pd/Ag Superatomic Nanoclusters.

The first 8-electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg19 (dtp)12 ] (dtp=S2 P(Oi Pr)2 - ) 1 and [PdHAg20 (dtp)12 ]+ 2 are reported. The targeted addition of a single Ag atom to 1 is achieved by the reaction of one equivalent of trifluoroacetic acid, resulting in the formation of 2 in 55 % yield. Further modification of the shell results in the formation of [PdAg21 (dtp)12 ]+ 3 via an internal redox reaction, with the system retaining an 8-electron superatomic configuration. The interstitial hydride in 1 and 2 contributes its 1s1 electron to the superatomic electron count and occupies a PdAg3 tetrahedron. The distributions of isomers corresponding to different dispositions of the outer capping Ag atoms are investigated by multinuclear VT NMR spectroscopy. The emissive state of 3 has a lifetime of 200 µs (λex =448; λem =842), while 1 and 2 are non-emissive. The catalytic reduction of 4-nitrophenol is demonstrated with 1-3 at room temperature.

Heptanuclear Silver Hydride Clusters as Catalytic Precursors for the Reduction of 4-Nitrophenol.

We report on the design, synthesis, and characterization of the first silver hydride clusters solely protected and stabilized by dithiophosphonate ligands and their application for the in situ generation of silver nanoparticles towards the catalytic reduction of 4-nitrophenol in an aqueous system. The synthesis of the silver monohydride cluster involves the incorporation of an interstitial hydride using sodium borohydride. Poly-nuclear magnetic resonance and mass spectrometry were used to establish the structural properties. The structural properties were then confirmed with a single-crystal X-ray diffraction analysis, which showed a distorted tetracapped tetrahedron core with one hydride ion encapsulated within the core of the silver framework. Additionally, the synthesized heptanuclear silver hydride was utilized as a precursor for the in situ generation of silver nanoparticles, which simultaneously catalyzed the reduction of 4-nitrophenol. The mechanism of the catalytic activity was investigated by first synthesizing AgNPs, which was subsequently used as a catalyst. The kinetic study showed that the pseudo-first constant obtained using the cluster (2.43 × 10-2 s-1) was higher than that obtained using the synthesized AgNPs (2.43 × 10-2 s-1). This indicated that the silver monohydride cluster was more active owing to the release of the encapsulated hydride ion and greater reaction surface prior to aggregation.

Solar inactivated Vibrio cholerae induces maturation of JAWS II dendritic cell line in vitro.

Solar disinfection (SODIS) has been shown to reduce the risk associated with the contraction of water borne diseases such as cholera. However, little or no research has been undertaken in exploring the role played by the immune system following the consumption of solar inactivated water pathogens. This study investigated the potential for solar inactivated Vibrio cholerae to induce the maturation of dendritic cells in vitro. Dendritic cells are professional antigen presenting cells found in mammals. However, only in their mature form are dendritic cells able to play their role towards a long lasting immune response. Three strains of V. cholerae were solar irradiated for 7 hours. Thereafter, the solar irradiated, non-solar irradiated, phosphate buffered saline prepared and heat/chemically inactivated cultures of V. cholerae as well as lipopolysaccharide and cholerae toxin-ß subunit were used to stimulate immature dendritic cells. After 48 hours, the dendritic cells were assessed for the expression of CD54, CD80, CD83, CD86, MHC-I and MHC-II cell surface markers. Results show that solar inactivated V. cholerae was able to induce maturation of the dendritic cells in vitro. These findings suggest that there may be an immunological benefit in consuming SODIS treated water.

Aqueous Route to Stable Luminescent Tetranuclear Copper(I) Dithiophosphonate Clusters.

A series of seven luminescent copper(I) dithiophosphonate (dtp) clusters of the type Cu4L4 (L = S2PR(OR')-) were formed from CuCl2·2H2O precursor in aqueous medium under ambient conditions. The dtp ligand serves the dual function of acting as a sacrificial reducing agent and cluster core stabilizer. The new clusters were characterized by 1H and 31P NMR and ESI-MS, and the single-crystal X-ray structures for two representative clusters [Cu4{(S2P(1,4-C6H4OMe)(OR')}4] (R' = OCH(CH3)2; CH2C6H5) were determined. The redox reaction yielded clusters in satisfactory yield, and all exhibited luminescence with λemmax in the range 519-534 nm and half-lives in the range 10-14 µs.

Characterization and structure prediction of partial length protein sequences of pcoA, pcoR and chrB genes from heavy metal resistant bacteria from the Klip River, South Africa.

The Klip River has suffered from severe anthropogenic effects from industrial activities such as mining. Long-term exposure to heavy metal pollution has led to the development of heavy metal resistant strains of Pseudomonas sp. KR23, Lysinibacillus sp. KR25, and E. coli KR29. The objectives of this study were to characterize the genetics of copper and chromate resistance of the isolates. Copper and chromate resistance determinants were cloned and sequenced. Open reading frames (ORFs) related to the genes CopA and CopR were identified in E. coli KR29, PcoA in Lysinibacillus sp. KR25 and none related to chromate resistance were detected. The 3D-models predicted by I-TASSER disclose that the PcoA proteins consist of ß-sheets, which form a part of the cupredoxin domain of the CopA copper resistance family of genes. The model for PcoR_29 revealed the presence of a helix turn helix; this forms part of a DNA binding protein, which is part of a heavy metal transcriptional regulator. The bacterial strains were cured using ethidium bromide. The genes encoding for heavy metal resistance and antibiotic resistance were found to be located on the chromosome for both Pseudomonas sp. (KR23) and E. coli (KR29). For Lysinibacillus (KR25) the heavy metal resistance determinants are suspected to be located on a mobile genetic element, which was not detected using gel electrophoresis.

Influence of solar water disinfection on immunity against cholera - a review.

Cholera remains a problem in developing countries. This is attributed to the unavailability of proper water treatment, sanitary infrastructure and poor hygiene. As a consequence, countries facing cholera outbreaks rely on interventions such as the use of oral rehydration therapy and antibiotics to save lives. In addition to vaccination, the provision of chlorine tablets and hygiene sensitization drives have been used to prevent new cholera infections. The implementation of these interventions remains a challenge due to constraints associated with the cost, ease of use and technical knowhow. These challenges have been reduced through the use of solar water disinfection (SODIS). The success of SODIS in mitigating the risk associated with the consumption of waterborne pathogens has been associated with solar irradiation. This has prompted a lot of focus on the solar component for enhanced disinfection. However, the role played by the host immune system following the consumption of solar-irradiated water pathogens has not received any significant attention. The mode of inactivation resulting from the exposure of microbiologically contaminated water results in immunologically important microbial states as well as components. In this review, the possible influence that solar water disinfection may have on the immunity against cholera is discussed.

Hydride-doped coinage metal superatoms and their catalytic applications.

Superatomic constructs have been identified as a critical component of future technologies. The isolation of coinage metal superatoms relies on partially reducing metallic frameworks to accommodate the mixed valent state required to generate a superatom. Controlling this reduction requires careful consideration in reducing the agent, temperature, and the ligand that directs the self-assembly process. Hydride-based reducing agents dominate the synthetic wet chemical routes to coinage metal clusters. However, within this category, a unique subset of superatoms that retain a hydride/s within the nanocluster post-reduction have emerged. These stable constructs have only recently been characterized in the solid state and have highly unique structural features and properties. The difficulty in identifying the position of hydrides in electron-rich metallic constructs requires the combination and correlation of several analytical methods, including ESI-MS, NMR, SCXRD, and DFT. This text highlights the importance of NMR in detecting hydride environments in these superatomic systems. Added to the complexity of these systems is the dual nature of the hydride, which can act as metallic hydrogen in some cases, resulting in entirely different physical properties. This review includes all hydride-doped superatomic nanoclusters emphasizing synthesis, structure, and catalytic potential.

The mineral manaksite, KNaMnSi4O10, as a supercapattery-type electrochemical energy storage material.

The manaksite mineral KNaMnSi4O10 was synthesized and used to fabricate electrodes, which were investigated for electrochemical energy storage (EES) application using cyclic voltammetry (CV), galvanostatic charge and discharge (GCD), and electrochemical impedance spectroscopy (EIS). Optimum weight percentages (wt%) of electrode components were established as 10 wt% polytetrafluoroethylene (PTFE) binder, 15 wt% RuO2 and 5 wt% carbon black. RuO2 was added to improve electrical conductivity. A ratio of 13 : 3 for KNaMnSi4O10 : RuO2 was used in the fabrication of the electrode. A study of the suitable electrolyte and corresponding concentration to use was done using NaOH and KOH, both at concentrations of 1 M, 3 M and 6 M, with 3 M NaOH as the optimum electrolyte and concentration. The KNaMnSi4O10 yielded a specific capacity of 106 mA h g-1. An investigation into the energy storage mechanism from a plot of log I(ν) vs. log ν, where I is current and ν is the scan rate gave a b value parameter of 0.8; that is, in-between 0.5 obtained for a pure battery material and 1.0 for a pure capacitor material. Accordingly, KNaMnSi4O10 exhibited a battery-supercapacitor duality phenomenon consistent with supercapattery materials. The KNaMnSi4O10 electrochemical system involved both capacitive and diffusion-controlled processes and was found to have good cyclic stability. It is concluded that KNaMnSi4O10 is a potential electrochemical energy storage material.

Effect of Eucomis autumnalis on the Osteogenic Differentiation of Adipose-Derived Stem Cells.

Eucomis autumnalis subsp. autumnalis (Mill.) Chitt. (EASA) is a commonly used medicinal plant for the treatment of fractures, osteoarthritis, back pain, and wound healing in Southern Africa. In this study, the effects of water and acetone extracts of EASA on the viability, osteogenic differentiation, and mineralization of human adipose-derived stem cells (hADSCs) were investigated in vitro. The results showed that both water and acetone extracts of EASA increased cell viability at concentrations between 10 and 50 µg/mL on day 7 and 14 of treatment. Osteogenic differentiation and mineralization of hADSCs were optimal at 5 µg/mL for the water extract and at 5-10 µg/mL for the acetone extract. A 5 µg/mL acetone extract upregulated the expression of the ALP, Runx2, Col1a1, and osteopontin genes. In addition, EASA upregulated ß-catenin, cyclin D1, and osteoprotegerin (OPG). The results suggest that EASA may likely upregulate the expression of ß-catenin, which subsequently upregulates the osteogenic marker genes through Runx2. However, EASA also upregulates cyclin D1 supporting the growth of precursor cells. Additionally, EASA upregulated the expression of OPG suggesting that it may inhibit bone resorption. The results of this study support the traditional use of the plant in bone healing. Impact statement Herbal remedies are used to treat various ailments by almost 80% of the developing world. Eucomis autumnalis is one of the most used medicinal plants in Southern Africa for the treatment of backache, osteoarthritis, and healing of fracture. There is a scarcity of scientific evidence to prove the efficacy of E. autumnalis for fracture repair. This study sought to assess the effect of the crude extracts in vitro and found that E. autumnalis promoted viability and osteogenic differentiation of human adipose-derived stem cells as demonstrated by biochemical and genetic markers. This medicinal plant could therefore have potential to regenerate bone tissue.

A construction guide for high-nuclearity (≥50 metal atoms) coinage metal clusters at the nanoscale: bridging molecular precise constructs with the bulk material phase.

Synthesis remains a major strength in chemistry and materials science and relies on the formation of new molecules and diverse forms of matter. The construction and identification of large molecules poses specific challenges and has historically lain in the realm of biological (organic)-type molecules with evolved synthesis methods to support such endeavours. But with the development of analytical tools such as X-ray crystallography, new synthesis methods toward large metal-based (inorganic) molecules and clusters have come to the fore, making it possible to accurately determine the precise distribution of hundreds of atoms in large clusters. In this review, we focus on different synthesis protocols used to form new metal clusters such as templating, alloying and size-focusing strategies. A specific focus is on group 11 metals (Cu, Ag, Au) as they currently predominate large metal cluster investigations and related Au and Ag bulk surface phenomena. This review focuses on metal clusters that have very high-nuclearity, i.e. with 50 or more metal centers within the isolated cluster. This size domain, it is believed, will become increasingly important for a variety of applications as these metal clusters are positioned at the interface between the molecular and bulk phases, whilst remaining a classic nanomaterial and retaining unique nano-sized properties.

Formation of dialysis-free Kombucha-based bacterial nanocellulose embedded in a polypyrrole/PVA composite for bulk conductivity measurements.

The preparation of dialysis-free bacterial nanocrystalline cellulose (BNCC) combined with a suitable polymer to form a robust conducting material remains a challenge. In this work, we developed a polypyrrole@BNCC/PVA nanocomposite that avoids the time-consuming dialysis step and which exhibits bulk electrical conductivity. The nanocellulose (NC) was derived from bacterial cellulose (BC) that was grown from a symbiotic colony of bacteria and yeast (SCOBY) starting from Kombucha tea, and then subjected to sulfuric acid hydrolysis that led to isolable bacterial nanocrystalline cellulose (BNCC) product and subsequently utilized as a stabilizer and support. Pyrrole monomer was reacted with FeCl3·6H2O as a polymerization initiator to form polypyrrole (PPy) and combined with BNCC it produced PPy@BNCC nanocomposite. We found PPy to BNCC in a 1 : 1 ratio provided the best suspension of the components and formed a well dispersed homogeneous network. The PPy@BNCC nanocomposite was then suspended in polyvinyl alcohol (PVA), that facilitated the construction of a continuous PPy@BNCC/PVA conductive network in the matrix. We designed an in-house electrical measurement apparatus and developed a method that recorded bulk resistance. The results obtained from the measurements of the electrical properties of the PPy@BNCC/PVA composite prepared dialysis-free were then compared with (i) a dialyzed sample of similar composition, and (ii) a traditional four-point probe measurement. The PPy@BNCC/PVA dialysis-free sample showed a higher conductivity compared to the dialyzed composite at 4.27 × 10-1 and 3.41 × 10-1 S m-1, respectively, and both values closely matched the traditional four-point probe measurement.

Advances in Regenerative Medicine and Tissue Engineering: Innovation and Transformation of Medicine.

Humans and animals lose tissues and organs due to congenital defects, trauma, and diseases. The human body has a low regenerative potential as opposed to the urodele amphibians commonly referred to as salamanders. Globally, millions of people would benefit immensely if tissues and organs can be replaced on demand. Traditionally, transplantation of intact tissues and organs has been the bedrock to replace damaged and diseased parts of the body. The sole reliance on transplantation has created a waiting list of people requiring donated tissues and organs, and generally, supply cannot meet the demand. The total cost to society in terms of caring for patients with failing organs and debilitating diseases is enormous. Scientists and clinicians, motivated by the need to develop safe and reliable sources of tissues and organs, have been improving therapies and technologies that can regenerate tissues and in some cases create new tissues altogether. Tissue engineering and/or regenerative medicine are fields of life science employing both engineering and biological principles to create new tissues and organs and to promote the regeneration of damaged or diseased tissues and organs. Major advances and innovations are being made in the fields of tissue engineering and regenerative medicine and have a huge impact on three-dimensional bioprinting (3D bioprinting) of tissues and organs. 3D bioprinting holds great promise for artificial tissue and organ bioprinting, thereby revolutionizing the field of regenerative medicine. This review discusses how recent advances in the field of regenerative medicine and tissue engineering can improve 3D bioprinting and vice versa. Several challenges must be overcome in the application of 3D bioprinting before this disruptive technology is widely used to create organotypic constructs for regenerative medicine.

Potential of Polycyclic Aromatic Hydrocarbon-Degrading Bacterial Isolates to Contribute to Soil Fertility.

Restoration of polycyclic aromatic hydrocarbon- (PAH-) polluted sites is presently a major challenge in agroforestry. Consequently, microorganisms with PAH-degradation ability and soil fertility improvement attributes are sought after in order to achieve sustainable remediation of polluted sites. This study isolated PAH-degrading bacteria from enriched cultures of spent automobile engine-oil polluted soil. Isolates' partial 16S rRNA genes were sequenced and taxonomically classified. Isolates were further screened for their soil fertility attributes such as phosphate solubilization, atmospheric nitrogen fixation, and indoleacetic acid (IAA) production. A total of 44 isolates were obtained and belong to the genera Acinetobacter, Arthrobacter, Bacillus, Flavobacterium, Microbacterium, Ochrobactrum, Pseudomonas, Pseudoxanthomonas, Rhodococcus, and Stenotrophomonas. Data analysed by principal component analysis showed the Bacillus and Ochrobactrum isolates displayed outstanding IAA production. Generalized linear modelling statistical approaches were applied to evaluate the contribution of the four most represented genera (Pseudomonas, Acinetobacter, Arthrobacter, and Rhodococcus) to soil fertility. The Pseudomonas isolates were the most promising in all three soil fertility enhancement traits evaluated and all isolates showed potential for one or more of the attributes evaluated. These findings demonstrate a clear potential of the isolates to participate in restorative bioremediation of polluted soil, which will enhance sustainable agricultural production and environmental protection.

The Effect of Solar Irradiated Vibrio cholerae on the Secretion of Pro-Inflammatory Cytokines and Chemokines by the JAWS II Dendritic Cell Line In Vitro.

The use of solar irradiation to sterilize water prior to its consumption has resulted in the reduction of water related illnesses in waterborne disease endemic communities worldwide. Currently, research on solar water disinfection (SODIS) has been directed towards understanding the underlying mechanisms through which solar irradiation inactivates the culturability of microorganisms in water, enhancement of the disinfection process, and the health impact of SODIS water consumption. However, the immunological consequences of SODIS water consumption have not been explored. In this study, we investigated the effect that solar irradiated V. cholerae may have had on the secretion of cytokines and chemokines by the JAWS II dendritic cell line in vitro. The JAWS II dendritic cell line was stimulated with the different strains of V. cholerae that had been: (i) prepared in PBS, (ii) inactivated through a combination of heat and chemical, (iii) solar irradiated, and (iv) non-solar irradiated, in bottled water. As controls, LPS (1 µg/ml) and CTB (1 µg/ml) were used as stimulants. After 48 hours of stimulation the tissue culture media from each treatment was qualitatively and quantitatively analysed for the presence of IL-1α, IL-1ß, IL-6, IL-7, IL-10, IL-12p40, IL-12p70, IL-15, MIP-1α, MIP-1ß, MIP-2, RANTES, TNF-α, IL-23 and IL-27. Results showed that solar irradiated cultures of V. cholerae induced dendritic cells to secrete significant (p<0.05) levels of pro-inflammatory cytokines in comparison to the unstimulated dendritic cells. Furthermore, the amount of pro-inflammatory cytokines secreted by the dendritic cells in response to solar irradiated cultures of V. cholerae was not as high as observed in treatments involving non-solar irradiated cultures of V. cholerae or LPS. Our results suggest that solar irradiated microorganisms are capable of inducing the secretion of pro-inflammatory cytokines and chemokines. This novel finding is key towards understanding the possible immunological consequences of consuming SODIS treated water.