Evaluation of the cytotoxicity of new formulations of cariostatic agents containing nano silver fluoride: an in vitro study.

The objective of the study was to assess the indirect cytotoxicity of 600 ppm and 1500 ppm nano silver fluoride (NSF) compared to other commercial cariostatic agents. 56 dentin discs with 0.4 mm in thickness were obtained from intact human molars and adapted to artificial pulp chambers (APCs). The discs were divided into seven groups according to treatment (n = 8): no treatment (positive control-PC), 29% hydrogen peroxide (negative control-NC), 30% Cariestop (CS30), 38% Riva Star (RS38), 38% Advantage Arrest (AA38), 600 ppm NSF (NSF600), and 1500 ppm NSF (NSF1500). The cariostatic agents were applied on the occlusal surface of the dentin discs (facing upward), and the pulp surface (facing downward) remained in contact with the culture medium. Immediately after the treatments, the extracts (DMEM + cariostatic agent components diffused through the discs) were collected and applied to MDPC-23 cells, which were assessed for viability (CV-alamarBlue, live/dead), adhesion/spreading (F-actin), alkaline phosphatase (ALP) activity, and mineralization nodule (MN) formation. The data were statistically analyzed by ANOVA/Games-Howell (p = 0.05). CV and ALP activity in CS30, RS38, AA38, and NSF600 were similar to PC (p > 0.05). MN formation significantly decreased only in NC, CS30, RS38, and AA38 compared to PC (p < 0.001). Only NSF600 and NSF1500 did not differ from PC (p > 0.05) with mineralization nodules, and this specific cell activity significantly decreased in all other groups (p < 0.05). NSF solutions (600 ppm and 1500 ppm) did not cause transdentinal toxicity on MDPC-23 cells.

Fabrication and Properties of the Montmorillonite/Nanobioglass Hybrid Reinforcement from Agroindustrial Waste for Bone Regeneration.

Nowadays, bone systems have a series of consequences that compromise the quality of life mainly due to wear and decreased bioactivity, generally in elderly people and children. In this context, the combination of montmorillonite (MMT-NPs) in a vitreous system such as nanobioglass facilitates the adsorption of biomolecules on the surface and within the interlamellar spaces, enabling the entry of ions by a cation exchange process focusing on increasing the rate of bone formation. This work aims to synthesize and characterize an eco-friendly hybrid reinforcement containing MMT-NPs with nanobioglass doped with magnesium nanoparticles (MgNPs-BV). In this way, MMT-NPs@MgNPs-BV was synthesized by the impregnation method, where an experimental design was used to verify the synthesis conditions. The ideal condition by experimental design was carried out in terms of the characterization and biological activity, where we demonstrated MMT-NPs of 30% w w-1, MgNPs-BV of 6% w w-1, and a calcination temperature of 1273.15 K with a cell viability around 66.87%, an average crystallite diameter of 12.5 nm, and a contact angle of 17.7°. The characterizations confirmed the impregnation method with an average particle size of 51.4 ± 13.1 nm. The mechanical tests showed a hardness of 2.6 GPa with an apparent porosity of 22.2%, similar to human bone. MMT-NPs@MgNPs-BV showed a cell proliferation of around 96% in osteoblastic cells (OFCOL II), with the formation of the apatite phase containing a relation of Ca/P of around 1.63, a biodegradability of 82%, and rapid release of ions with a Ca/P ratio of 1.42. Therefore, the eco-friendly hybrid reinforcement with MMT-NPs and MgNPs-BV shows potential for application with a matrix for biocompatible nanocomposites for bone regeneration.

Efficacy of a high concentration of nano silver fluoride in preventing caries: A randomized controlled trial.

Background: To investigate the effectiveness of a novel agent containing Nano Silver Fluoride 1500 (NSF 1500) and chitosan to inactivate carious lesions in children. Material and Methods: The study included eighty children. While both groups had fluoride dentifrice applied to their teeth, only the experimental group received treatment with the NSF 1500-ppm solution. The first and sixth-month interval examinations were conducted by two calibrated dentists (k = 0.85). Results: The NSF 1500 group had 69.2% of their teeth with arrested decay, while the control group had 24.1%. The difference was statistically significant (p 0.001), with a preventive fraction of 59.4%. The number needed to treat (NNT) was approximately two. The NSF 1500 formulation was more effective than toothbrushing alone with fluoridated dentifrice in preventing dental caries. Conclusions: The effectiveness of NSF 1500 is determined by the size and depth of the dental cavity. Its ability to arrest caries lesions was comparable to previously tested products, NSF 400 and NSF 600. Key words:Preventive dentistry, dental caries, nanoparticles.

The emerging chemistry of self-electrified water interfaces.

Water is known for dissipating electrostatic charges, but it is also a universal agent of matter electrification, creating charged domains in any material contacting or containing it. This new role of water was discovered during the current century. It is proven in a fast-growing number of publications reporting direct experimental measurements of excess charge and electric potential. It is indirectly verified by its success in explaining surprising phenomena in chemical synthesis, electric power generation, metastability, and phase transition kinetics. Additionally, electrification by water is opening the way for developing green technologies that are fully compatible with the environment and have great potential to contribute to sustainability. Electrification by water shows that polyphasic matter is a charge mosaic, converging with the Maxwell-Wagner-Sillars effect, which was discovered one century ago but is still often ignored. Electrified sites in a real system are niches showing various local electrochemical potentials for the charged species. Thus, the electrified mosaics display variable chemical reactivity and mass transfer patterns. Water contributes to interfacial electrification from its singular structural, electric, mixing, adsorption, and absorption properties. A long list of previously unexpected consequences of interfacial electrification includes: "on-water" reactions of chemicals dispersed in water that defy current chemical wisdom; reactions in electrified water microdroplets that do not occur in bulk water, transforming the droplets in microreactors; and lowered surface tension of water, modifying wetting, spreading, adhesion, cohesion, and other properties of matter. Asymmetric capacitors charged by moisture and water are now promising alternative equipment for simultaneously producing electric power and green hydrogen, requiring only ambient thermal energy. Changing surface tension by interfacial electrification also modifies phase-change kinetics, eliminating metastability that is the root of catastrophic electric discharges and destructive explosions. It also changes crystal habits, producing needles and dendrites that shorten battery life. These recent findings derive from a single factor, water's ability to electrify matter, touching on the most relevant aspects of chemistry. They create tremendous scientific opportunities to understand the matter better, and a new chemistry based on electrified interfaces is now emerging.

Water Reactivity in Electrified Interfaces: The Simultaneous Production of Electricity, Hydrogen, and Hydrogen Peroxide at Room Temperature.

Hygroelectric cells deliver hydrogen, hydrogen peroxide, and electric current simultaneously at room temperature from liquid water or vapor. Different cell arrangements allowed the electrical measurements and the detection and measurement of the reaction products by two methods each. Thermodynamic analysis shows that water dehydrogenation is a non-spontaneous reaction under standard conditions, but it can occur within an open, non-electroneutral system, thus supporting the experimental results. That is a new example of chemical reactivity modification in charged interfaces, analogous to the hydrogen peroxide formation in charged aqueous aerosol droplets. Extension of the experimental methods and the thermodynamic analysis used in this work may allow the prediction of interesting new chemical reactions that are otherwise unexpected. On the other hand, this adds a new facet to the complex behavior of interfaces. Hygroelectric cells shown in this work are built from commodity materials, using standard laboratory or industrial processes that are easily scaled up. Thus, hygroelectricity may eventually become a source of energy and valuable chemicals.

Advanced Hydrogels Combined with Silver and Gold Nanoparticles against Antimicrobial Resistance.

The development of multidrug-resistant (MDR) microorganisms has increased dramatically in the last decade as a natural consequence of the misuse and overuse of antimicrobials. The World Health Organization (WHO) recognizes that this is one of the top ten global public health threats facing humanity today, demanding urgent multisectoral action. The UK government foresees that bacterial antimicrobial resistance (AMR) could kill 10 million people per year by 2050 worldwide. In this sense, metallic nanoparticles (NPs) have emerged as promising alternatives due to their outstanding antibacterial and antibiofilm properties. The efficient delivery of the NPs is also a matter of concern, and recent studies have demonstrated that hydrogels present an excellent ability to perform this task. The porous hydrogel structure with a high-water retention capability is a convenient host for the incorporation of the metallic nanoparticles, providing an efficient path to deliver the NPs properly reducing bacterial infections caused by MDR pathogenic microorganisms. This article reviews the most recent investigations on the characteristics, applications, advantages, and limitations of hydrogels combined with metallic NPs for treating MDR bacteria. The mechanisms of action and the antibiofilm activity of the NPs incorporated into hydrogels are also described. Finally, this contribution intends to fill some gaps in nanomedicine and serve as a guide for the development of advanced medical products.

Synthesis and characterization of nanozeolite from (agro)industrial waste for application in heterogeneous photocatalysis.

The pollution of wastewater with dyes has become a serious environmental problem around the world. In this context, the work aims to synthesize and characterize a supported nanocatalyst (NZ-180) from rice husk (RH) and alum sludge (AS) incorporating silver (AgNPs@NZ-180) and titanium nanoparticles (TiNPs@NZ-180) for Rhodamine B (RhB) dye degradation, under UV and visible irradiation. Central rotatable composite design (CRCD) was used to determine ideal conditions, using nanocatalyst and dye concentration such as input variables and degradation percentage like response variable. Samples were characterized by XRD, SEM-EDS, N2 porosimetry, DLS, and zeta potential analyses. TiNPs@NZ-180 showed the best photocatalytic activity (62.62 and 50.82% under UV and visible irradiation, respectively). Specific surface area has increased from 35.90 to 418.90 m2 g-1 for NZ-180 and TiNPs@NZ-180, respectively. Photocatalytic performance of TiNPs@NZ-180 has reduced to 8 and 10% after 5 cycles under UV and visible light irradiation. Ideal conditions found by CRCD were 2.75 g L-1 and 20 mg L-1 for nanocatalyst and RhB concentrations, respectively. Therefore, (agro)industrial waste present such an alternative material for application in the removal of wastewater with dyes, which helps in the reduction of the impact of chemicals/pollutants on human and animal health.

Catheter Reprocessing for Coronary Angiography: It is Not Safe.

BACKGROUND: Coronary angiography and percutaneous coronary intervention are frequently and increasingly performed worldwide. Although catheters for coronary angiography are considered as single-use devices, some people still question this decision. This study evaluated the structural characteristics and thermal stability of new and reprocessed catheters. METHODS: Five catheters (Judkins left) of the same brand and manufacturer were selected for each analysis. We evaluated: new catheters, catheters reprocessed once (first), twice (second), thrice (third), and seven times (seventh). The optical analyses of the proximal, middle and distal parts of the catheters were performed by magnifying glass. Besides, thermogravimetric analyses were done. RESULTS: After reprocessing, the crushing, color changes, folds, dents, deformations, and lumen narrowing were observed; the stainless-steel framework, the external tortuosity, the interlaced mesh of stainless-steel wires and loss of polymeric material were visualized. Thermogravimetric analysis showed lost of mass of the catheters. CONCLUSIONS: This study demonstrated that the structural integrity and mass of catheters are lost with reprocessing. These findings may be caused by several steps of reprocessing; however, regardless of which step or steps were responsible, the presence of structural integrity loss leads to the recommendation of not reusing this type of device.

Reprocessing of Catheters Used for Coronary Angiography and Changes in the Polymeric Structures.

BACKGROUND: Catheters are extensively used for coronary angiographies. These devices are long, thin, and flexible tubes of variable diameters that are made of the following polymer compounds: polyamide, polyurethane and Teflon. The objectives of this study are to identify changes that occur in the polymeric structure of the catheters, including an analysis of microcracks, fissures, cuts, perforations, roughness, and porosity in the internal and external layers after the first, second, third, and seventh reprocessing. METHODS: Five catheters of the same brand and manufacturer were selected for each analysis, except for the new and seventh catheters, which had only one sample. The catheters that we analyzed included new catheters, catheter reprocessed once (1st), catheters reprocessed twice (2nd), catheters reprocessed three times (3rd), and catheters reprocessed up to seven times (7th). Samples were cut into small pieces and the scanning electron microscope and infrared spectroscopy were used for analysis. RESULTS: Scanning electron microscopy (SEM) of reprocessed catheters revealed rougher surface with porosity, stainless steel wires, peeling of the inner layers, micropores, small holes, disordered cracks, cracks, grooves, microcracks, granular appearance, dots whitish, diffuse microcracks, desquamation, diffuse recesses, depressions, protrusions and deep crevices. Infrared spectroscopy suggested a possible change in the chemical structures of the polymer. There was a directly proportional relationship between the reprocessing number and the carbonyl ratio. CONCLUSIONS: The combined SEM and infrared analyses reveal that reprocessing damages the integrity of coronary angiography catheters. Therefore, the reprocessing of such catheters is not recommended.

Effects of a New Nano-Silver Fluoride-Containing Dentifrice on Demineralization of Enamel and Streptococcus mutans Adhesion and Acidogenicity.

An experimental dentifrice containing nano-silver fluoride (NSF) and a sodium fluoride (NaF) toothpaste were tested in vitro, against S. mutans, to evaluate the minimal inhibitory concentration (MIC), minimal bactericidal concentration (MBC), antiadherence, antiacid, enamel microhardness, and OCT. The microdilution technique was used to determine the MIC and MBC. Fragments of deciduous enamel were treated with dentifrice slurries, containing bacterial suspension and PBS-treated saliva. The quantification of the microorganisms that adhered to the enamel was determined after 24 hours of incubation, and media pH readings were performed after 2 hours and 24 hours. Deciduous teeth were evaluated for microhardness and OCT during 14 days of pH cycling. Data were statistically analyzed using Student's t-test, Mann-Whitney U test, ANOVA, and Tukey tests at 5% of significance. Dentifrices containing NSF presented a lower MIC and higher statistically significant results compared to NaF dentifrices with respect to preventing bacterial adhesion and pH decreases. NSF and NaF dentifrices showed the same ability to avoid enamel demineralization corroborated by the OCT images. The NSF formulation had a better antibacterial effect compared to NaF dentifrices and similar action on the demineralization of enamel indicating their potential effectiveness to prevent caries.

Conversion of "Waste Plastic" into Photocatalytic Nanofoams for Environmental Remediation.

Plastic debris is a major environmental concern, and to find effective ways to reuse polystyrene (PS) presents major challenges. Here, it is demonstrated that polystyrene foams impregnated with SnO2 are easily generated from plastic debris and can be applied to photocatalytic degradation of dyes. SnO2 nanoparticles were synthesized by a polymeric precursor method, yielding specific surface areas of 15 m2/g after heat treatment to 700 °C. Crystallinity, size, and shape of the SnO2 particles were assessed by X-ray diffraction (XRD) and transmission electron microscopy (TEM), demonstrating the preparation of crystalline spherical nanoparticles with sizes around 20 nm. When incorporated into PS foams, which were generated using a thermally induced phase separation (TIPS) process, the specific surface area increased to 48 m2/g. These PS/SnO2 nanofoams showed very good efficiency for photodegradation of rhodamine B, under UV irradiation, achieving up to 98.2% removal. In addition the PS/SnO2 nanofoams are shown to retain photocatalytic activity for up to five reuse cycles.

AgNPs: The New Allies Against S. Mutans Biofilm - A Pilot Clinical Trial and Microbiological Assay.

The purpose of this study was to evaluate the antimicrobial properties of a new formulation containing silver nanoparticles, named Nano Silver Fluoride (NSF), to inhibit Streptococcus mutans biofilm formation on children's dental enamel. The variations in dental biofilm pH and in the Simplified-Oral-Hygiene-Index (OHI-S) also were evaluated after the treatment with NSF. This was a randomized, double-blind, crossover and prospective pilot clinical trial study in which 12 schoolchildren, aged between 7-8 years, had their dental enamel treated with two solutions: S1 - Nano Silver Fluoride and S2 - negative control (saline solution), in different experimental moments. The dental biofilm adhered to enamel treated with NSF had lower values of S. mutans viability (absorbance) and colony forming units (CFU) than the S0 (baseline) and S2. There was a statistically significant difference between the OHI-S mean values of S0 and S1. There were no differences between the biofilm pH (both before and after the use of the test substances) and among the different groups. These properties suggest that NSF has bactericidal effect against S. mutans biofilm and it may be used for clinical control and prevention of dental biofilm formation.

Silver nanoparticles in dentistry.

OBJECTIVE: Silver nanoparticles (AgNPs) have been extensively studied for their antimicrobial properties, which provide an extensive applicability in dentistry. Because of this increasing interest in AgNPs, the objective of this paper was to review their use in nanocomposites; implant coatings; pre-formulation with antimicrobial activity against cariogenic pathogens, periodontal biofilm, fungal pathogens and endodontic bacteria; and other applications such as treatment of oral cancer and local anesthesia. Recent achievements in the study of the mechanism of action and the most important toxicological aspects are also presented. METHODS: Systematic searches were carried out in Web of Science (ISI), Google, PubMed, SciFinder and EspaceNet databases with the keywords "silver nano* or AgNP*" and "dentist* or dental* or odontol*". RESULTS: A total of 155 peer-reviewed articles were reviewed. Most of them were published in the period of 2012-2017, demonstrating that this topic currently represents an important trend in dentistry research. In vitro studies reveal the excellent antimicrobial activity of AgNPs when associated with dental materials such as nanocomposites, acrylic resins, resin co-monomers, adhesives, intracanal medication, and implant coatings. Moreover, AgNPs were demonstrated to be interesting tools in the treatment of oral cancers due to their antitumor properties. SIGNIFICANCE: The literature indicates that AgNPs are a promising system with important features such as antimicrobial, anti-inflammatory and antitumor activity, and a potential carrier in sustained drug delivery. However, there are some aspects of the mechanisms of action of AgNPs, and some important toxicological aspects arising from the use of this system that must be completely elucidated.

AgNPs: The New Allies Against S. Mutans Biofilm - A Pilot Clinical Trial and Microbiological Assay

Abstract: The purpose of this study was to evaluate the antimicrobial properties of a new formulation containing silver nanoparticles, named Nano Silver Fluoride (NSF), to inhibit Streptococcus mutans biofilm formation on children's dental enamel. The variations in dental biofilm pH and in the Simplified-Oral-Hygiene-Index (OHI-S) also were evaluated after the treatment with NSF. This was a randomized, double-blind, crossover and prospective pilot clinical trial study in which 12 schoolchildren, aged between 7-8 years, had their dental enamel treated with two solutions: S1 - Nano Silver Fluoride and S2 - negative control (saline solution), in different experimental moments. The dental biofilm adhered to enamel treated with NSF had lower values of S. mutans viability (absorbance) and colony forming units (CFU) than the S0 (baseline) and S2. There was a statistically significant difference between the OHI-S mean values of S0 and S1. There were no differences between the biofilm pH (both before and after the use of the test substances) and among the different groups. These properties suggest that NSF has bactericidal effect against S. mutans biofilm and it may be used for clinical control and prevention of dental biofilm formation.

Resumo O objetivo do presente estudo foi avaliar as propriedades antimicrobianas de uma nova formulação composta por nanopartículas de prata, denominada nano silver fluoride (NSF), na inibição de biofilme de Streptococcus mutans sobre a superfície do esmalte dentário de crianças. Variações no pH do biofilme dental e nos valores do índice de Higiene Oral Simplificada (IHO-S) também foram avaliadas após o tratamento com NSF. Trata-se de um estudo piloto, randomizado, duplo cego, cruzado e prospectivo. A amostra foi composta por 12 crianças, de ambos os gêneros, com idades entre 7 e 8 anos, as quais utilizaram as duas soluções testes, S1- NSF e S2- controle negativo (solução salina). O biofilme dental tratado com NSF apresentou menores valores de viabilidade de S. mutans (absorbância) e de unidades formadoras de colônias (UFC) do que o biofilme baseline e o biofilme tratado com S2. Houve diferença estatisticamente significativa entre os valores médios de IHO-S dos grupos baseline e S1, com uma redução dos valores. Não houve qualquer variação nos valores de pH do biofilme dental, antes e depois do tratamento com S1 e S2 e entre os diferentes grupos. Estas propriedades sugerem que NSF possui efeito bactericida sobre o biofilme de S. mutans, podendo ser utilizado clinicamente para o controle e prevenção da formação do biofilme dentário.

Potentiometric perchlorate determination at nanomolar concentrations in vegetables.

In this work, an expeditious method based on the multi-commutated flow-analysis concept with potentiometric detection is proposed to perform determinations of the emergent contaminant perchlorate in vegetable matrices down to nanomolar concentration. To accomplish the task, a tubular shaped potentiometric sensor selective to perchlorate ion was constructed with a PVC membrane containing 12mmol/kg of the polyamine bisnaphthalimidopropyl-4,4'-diaminodiphenylmethane and 2-nitrophenyl phenyl ether 68% (w/w) as plasticizer casted on a conductive epoxy resin. Under optimal flow conditions, the sensor responded linearly in the concentration range of 6.3×10-7-1.0×10-3mol/L perchlorate. In order to extend the determinations to lower concentrations (4.6(±1.3)×10-10mol/L perchlorate), a column packed with 70mg of sodium 2,5,8,11,14-pentaoxa-1-silacyclotetradecane-polymer was coupled to the flow-system thus enabling prior pre-concentration of the perchlorate. The proposed procedure provides a simpler alternative for the determination of perchlorate in foods, nowadays only allowed by sophisticated and expensive equipment and laborious methods.

Antimicrobial and cytotoxicity evaluation of colloidal chitosan - silver nanoparticles - fluoride nanocomposites.

The present study aimed to evaluate the antimicrobial activity and cytotoxicity of colloidal chitosan - silver nanoparticle - fluoride nanocomposites (CChAgNpFNc), with different silver nanoparticle shapes and sizes. The syntheses of CChAgNpFNc were performed with silver nitrate added to a chitosan solution, addition of a sodium borohydride solution and solid sodium fluoride. Solution of ascorbic acid was added to synthesize larger silver nanoparticles. CChAgNpFNc obtained: S1- 100% spherical, 8.7±3.1nm; S2- 97% spherical, 15.0±7.9nm and 2.5% triangular, 22.2±9.5nm; S3- 77.3% spherical, 31.8±10.4nm, 15.9% triangular, 27.1±10.1nm and 6.8% elliptical, 33.2±7.8nm; and S4- 75.2% spherical, 43.2±14.3nm; 23.3% triangular 38.2±14.8nm, and 1.5% elliptical 38.4±11.6nm. The CChAgNpFNc showed antimicrobial activity against Staphylococcus aureus, Escherichia coli, Enterococcus faecalis, Pseudomonas aeruginosa and Candida albicans, by microdilution technique. The influence on the growth of microorganisms was evaluated using a fluorescence assay, and showed an increasing lag phase and a decreasing log phase. Cytotoxicity was investigated using Artemia salina and MTT assays. The S3 and S4 samples exhibited low cytotoxicity. The S1 and S2 samples inhibited murine macrophages and revealed lethal dose concentrations above 1000mg/mL that were classified as moderately toxic. Thus, CChAgNpFNc are potential options for the control of multiple-drug-resistant microorganisms and do not represent substantial risks to human health.

Antimicrobial activity of silver nanoparticles in treating dental caries / Atividade antimicrobiana de nanopartículas de prata no tratamento da cárie dentária

Objective: to clarify the benefits related to the use of silver nanoparticles (AgNPs) in the prevention of dental caries in children, we compared the antibacterial pro-perties of silver nanoparticles, chlorhexidine, and silver diamine fluoride (SDF) to Streptococcus mutans. Mate-rials and method: to analyze the minimum inhibitory concentration (MIC) we used the spectrophotometric microdilution method (SMM), and turbidity. We also verified the minimum bactericidal concentration (MBC) of the target products. Analysis of variance (ANOVA) was used to compare MIC and MBC among the groups studied. Results: regarding antimicrobial proprieties, the tested substances showed effective bacteriostatic and bactericide activity. The silver nanoparticles had the lowest value of MIC against reference strains (ATCC 25175) (p < 0.05). In clinical strains, the MIC value of silver nanoparticles was comparable to that of chlorhe-xidine (p > 0.05), and lower than SDF (p < 0.05). Con-clusion: silver nanoparticles proved to have antimicro-bial activity against S. mutans, therefore, they may be an effective agent in the prevention of dental caries

Photoreactive surfactants: a facile and clean route to oxide and metal nanoparticles in reverse micelles.

A new class of photoreactive surfactants (PRSs) is presented here, consisting of amphiphiles that can also act as reagents in photochemical reactions. An example PRS is cobalt 2-ethylhexanoate (Co(EH)(2)), which forms reverse micelles (RMs) in a hydrocarbon solvent, as well as mixed reversed micelles with the standard surfactant Aerosol-OT (AOT). Small-angle neutron scattering (SANS) data show that mixed AOT/PRS RMs have a spherical structure and size similar to that of pure AOT micelles. Excitation of the ligand-to-metal charge transfer (LMCT) band in the PRSs promotes electron transfer from PRS to associated metal counterions, leading to the generation of metal and metal-oxide nanoparticles inside the RMs. This work presents proof of concept for employing PRSs as precursors to obtain nearly monodisperse inorganic nanoparticles: here both Co(3)O(4) and Bi nanoparticles have been synthesized at high metal concentration (10(-2) M) by simply irradiating the RMs. These results point toward a new approach of photoreactive self-assembly, which represents a clean and straightforward route to the generation of nanomaterials.

Modeling, structural, and spectroscopic studies of lanthanide-organic frameworks.

In this paper, we report the hydrothermal synthesis of three lanthanide-organic framework materials using as primary building blocks the metallic centers Eu(3+), Tb(3+), and Gd(3+) and residues of mellitic acid: [Ln(2)(MELL)(H(2)O)(6)] (where Ln(3+) = Eu(3+), Tb(3+), and Gd(3); hereafter designated as (1), (2) and (3)). Structural characterization encompasses single-crystal X-ray diffraction studies, thermal analysis, and vibrational spectroscopy, plus detailed investigations on the experimental and predicted (using the Sparkle/AM1 model) photophysical luminescent properties. Crystallographic investigations showed that the compounds are all isostructural, crystallizing in the orthorhombic space group Pnnm and structurally identical to the lanthanum 3D material reported by the group of Williams. (2) is highly photoluminescent, as confirmed by the measured quantum yield and lifetime (37% and 0.74 ms, respectively). The intensity parameters (Omega(2), Omega(4), and Omega(6)) of (1) were first calculated using the Sparkle/AM1 structures and then employed in the calculation of the rates of energy transfer (W(ET)) and back-transfer (W(BT)). Intensity parameters were used to predict the radiative decay rate. The calculated quantum yield derived from the Sparkle/AM1 structures was approximately 16%, and the experimental value was 8%. We attribute the registered differences to the fact that the theoretical model does not consider the vibronic coupling with O-H oscillators from coordinated water molecules. These results clearly attest for the efficacy of the theoretical models employed in all calculations and open a new window of interesting possibilities for the design in silico of novel and highly efficient lanthanide-organic frameworks.

Macrocrystal Swelling: AFM in Situ Observation of Particle and Film Deformation and Motion.

The surface of a poly(styrene-hydroxyethylmethacrylate), macrocrystalline film was observed by atomic force microscopy in the contact mode, before and during film immersion in water. The swelling effect on film morphology is strongly dependent on the quality of the macrocrystalline surface: film integrity is preserved or concerted many-particle displacement is observed in well-organized areas with few defects, but extensive particle displacement is observed in highly defective areas. The lateral particle dimensions increase by ca. 10-15% only and particle aspect ratio is unaltered in the highly crystalline areas. However, film roughness is greatly decreased, and flat mirror-like surface domains are obtained due to the concerted effects of particle swelling and latex-water interfacial tension. Copyright 2001 Academic Press.