Developing Carrier Complexes for “Caged NO”: RuCl3(NO)(H2O)2 Complexes of Dipyridylamine, (dpaH), N,N,N'N'-Tetrakis (2-Pyridyl) Adipamide, (tpada), and (2-Pyridylmethyl) Iminodiacetate, (pida2-)

Delivery agents which can carry the {Ru(NO)}6 chromophore (“caged NO”) are desired for vasodilation and for photodynamic therapy of tumors. Toward these goals, complexes derived from [RuCl3(NO)(H2O)2]= (1) have been prepared using dipyridylamine (dpaH) as mono and bis adducts, [Ru(NO)Cl3(dpaH)] = (2) and [Ru(NO)Cl(dpaH)2]Cl2 = (3). The dpaH ligands coordinate cis to the Ru(NO) axis.The mono derivative is a model for a potential DNA groove-spanning binuclear complex {[RuNO)Cl3]2(tpada)} = (4) which has two DNA-coordinating RuII centers, photo-labile {Ru(NO)}6 sites, and a groove-spanning tether moiety.The binuclear assembly is prepared from the tethered dipyridylamine ligand N,N,N',N'-tetrakis(2-pyridylmethyl)adipamide (tpada) which has recently been shown to provide a binuclear carrier complex suited to transporting RuII and PdII agents. A related complex, [Ru(NO)Cl(pida)] = (5) with the {Ru(NO)}6 moiety bound to (2-pyridylmethyl) iminodiacetate (pida2-) is also characterized as a potential “caged NO” carrier. Structural information concerning the placement of the pyridyl donor groups relative to the {Ru(NO)}6 unit has been obtained from 1H and 13C NMR and infrared methods, noting that a pyridyl donor trans to NO+ causes “trans strengthening” of this ligand for [Ru(NO)Cl(pida)], whereas placement of pyridyl groups cis to NO+ causes a weakening of the N-O bond and a lower NO stretching frequency in the dpa-based complexes

Preparation of hexagonal GeO2 particles with particle size and crystallinity controlled by peptides, silk and silk-peptide chimeras

We demonstrate the use of silk based proteins to control the particle/crystallite size during GeO2 formation, using a bio-mimetic approach at circumneutral pH and ambient temperature. Multicrystalline GeO2 was prepared from germanium tetraethoxide (TEOG) in the presence of different silk-based proteins: Bombyx mori silk (native silk) and two chimeric proteins prepared by linking a germania binding peptide (Ge28: HATGTHGLSLSH) with Bombyx mori silk via chemical coupling at different peptide loadings (silk-Ge28 10% and silk-Ge28 50%). The mineralisation activity of the silk-based proteins was compared with that of peptide Ge28 as a control system. GeO2 mineralisation was investigated in water and in citric acid/bis-tris propane buffer at pH 6. Morphology, particle size, crystallinity, water and organic content of the materials obtained were analysed to study the effect of added biomolecules and mineralisation environment on material properties. In the presence of silk additives well-defined cube-shape hybrid materials composed of hexagonal germania and up to ca. 5 wt% organic content were obtained. The cubic particles ranged from 0.4 to 1.4m in size and were composed of crystalline domains in the range 35-106 nm depending on the additive used and synthesis conditions

Biomimetic Synthesis of Gelatin Polypeptide-Assisted Noble-Metal Nanoparticles and Their Interaction Study

Herein, the generation of gold, silver, and silver–gold (Ag–Au) bimetallic nanoparticles was carried out in collagen (gelatin) solution. It first showed that the major ingredient in gelatin polypeptide, glutamic acid, acted as reducing agent to biomimetically synthesize noble metal nanoparticles at 80°C. The size of nanoparticles can be controlled not only by the mass ratio of gelatin to gold ion but also by pH of gelatin solution. Interaction between noble-metal nanoparticles and polypeptide has been investigated by TEM, UV–visible, fluorescence spectroscopy, and HNMR. This study testified that the degradation of gelatin protein could not alter the morphology of nanoparticles, but it made nanoparticles aggregated clusters array (opposing three-dimensional α-helix folding structure) into isolated nanoparticles stabilized by gelatin residues. This is a promising merit of gelatin to apply in the synthesis of nanoparticles. Therefore, gelatin protein is an excellent template for biomimetic synthesis of noble metal/bimetallic nanoparticle growth to form nanometer-sized device

PRADA: Portable Reusable Accurate Diagnostics with nanostar Antennas for multiplexed biomarker screening

Precise monitoring of specific biomarkers in biological fluids with accurate biodiagnostic sensors is critical for early diagnosis of diseases and subsequent treatment planning. In this work, we demonstrated an innovative biodiagnostic sensor, portable reusable accurate diagnostics with nanostar antennas (PRADA), for multiplexed biomarker detection in small volumes (~50 μl) enabled in a microfluidic platform. Here, PRADA simultaneously detected two biomarkers of myocardial infarction, cardiac troponin I (cTnI), which is well accepted for cardiac disorders, and neuropeptide Y (NPY), which controls cardiac sympathetic drive. In PRADA immunoassay, magnetic beads captured the biomarkers in human serum samples, and gold nanostars (GNSs) “antennas” labeled with peptide biorecognition elements and Raman tags detected the biomarkers via surface‐enhanced Raman spectroscopy (SERS). The peptide‐conjugated GNS‐SERS barcodes were leveraged to achieve high sensitivity, with a limit of detection (LOD) of 0.0055 ng/ml of cTnI, and a LOD of 0.12 ng/ml of NPY comparable with commercially available test kits. The innovation of PRADA was also in the regeneration and reuse of the same sensor chip for ~14 cycles. We validated PRADA by testing cTnI in 11 de‐identified cardiac patient samples of various demographics within a 95% confidence interval and high precision profile. We envision low‐cost PRADA will have tremendous translational impact and be amenable to resource‐limited settings for accurate treatment planning in patients

Review on nanoparticles and nanostructured materials: History, sources, toxicity and regulations

Nanomaterials (NMs) have gained prominence in technological advancements due to their tunable physical, chemical and biological properties with enhanced performance over their bulk counterparts. NMs are categorized depending on their size, composition, shape, and origin. The ability to predict the unique properties of NMs increases the value of each classification. Due to increased growth of production of NMs and their industrial applications, issues relating to toxicity are inevitable. The aim of this review is to compare synthetic (engineered) and naturally occurring nanoparticles (NPs) and nanostructured materials (NSMs) to identify their nanoscale properties and to define the specific knowledge gaps related to the risk assessment of NPs and NSMs in the environment. The review presents an overview of the history and classifications of NMs and gives an overview of the various sources of NPs and NSMs, from natural to synthetic, and their toxic effects towards mammalian cells and tissue. Additionally, the types of toxic reactions associated with NPs and NSMs and the regulations implemented by different countries to reduce the associated risks are also discussed

ФОРМИРОВАНИЕ ПРОЕКТИВНОГО ПОКРЫТИЯ ГАЗОННОГО ТРАВОСТОЯ ПРИ ПРИМЕНЕНИИ МИНЕРАЛЬНЫХ И КРЕМНИЙСОДЕРЖАЩИХ УДОБРЕНИЙ

Silicon containing fertilizer “Siliplant” and mineral fertilizers are established to influence ornamental traits of lawn herbage. Increased projective covering of lawn herbage – meadow grass and red fes-cue – is marked with the preparation “Siliplant” and mineral fertilizers applied, particularly with their joint application. In the first and second years of research in dry and excessively humid vegetation periods the optimal results were obtained through the joint treatment with mineral fertilizers and the preparation “Siliplant”: the projective covering increased in the year of sowing by averaged 27.5 % in meadow grass and 25 % in red fescue versus the control, in the second year the covering went up by averaged 19.7 and 8.44 %, respectively. Mineral fertilizers applied increased the projective covering in the year of sowing on average by 22.5 % in meadow grass and by 20 % in red fescue, in the second year they did by 14.7 % and 6.25 %, respectively. The treatment with the silicon-containing preparation “Siliplant” increased the projective covering in the year of sowing by averaged 15 % in meadow grass and by 7.5 % in red fescue; in the second vegetation period the averaged effect of the treatment was by 6.58 and 1.51 % higher, respectively.Установлено влияние кремнийсодержащего удобрения «Силиплант» и минеральных удобрений на декоративные качества газонного травостоя. Отмечено увеличение проективного покрытия газонных травостоев мятлика лугового и овсяницы красной при применении препарата «Силиплант» и минеральных удобрений, особенно при их совместном использовании. В  первый и второй годы исследований при засушливом и избыточно влажном вегетационном периоде оптимальные результаты получены при применении минеральных удобрений совместно с препаратом «Силиплант»: проективное покрытие увеличивалось в год посева в среднем на 27,5% у мятлика лугового и на 25% у овсяницы красной по отношению к контролю, во второй год – на 19,7 и 8,44% соответственно. Применение минеральных удобрений увеличивало проективное покрытие в год посева в среднем на 22,5% у мятлика лугового и на 20% у овсяницы красной, во второй год на 14,7 и 6,25% соответственно. Применение кремнийсодержащего препарата «Силиплант» увеличивало проективное покрытие в год посева в среднем на 15% у мятлика лугового и на 7,5% у овсяницы красной; во втором вегетационном периоде на 6,58 и на 1,51% соответственно

Thermodynamic study of interactions between ZnO and ZnO binding peptides using isothermal titration calorimetry

Whilst material specific peptide binding sequences have been identified using a combination of combinato-rial methods and computational modelling tools, a deep molecular level understanding of the fundamental principles through which these interactions occur and in some instances modify the morphology of inorganic materials is far from being fully realized. Understanding the thermodynamic changes that occur during peptide-inorganic interactions and correlating these to structural modifications of the inorganic materials could be the key to achieving and mastering con-trol over material formation processes. This study is a detailed investigation applying isothermal titration calorimetry (ITC) to directly probe thermodynamic changes that occur during interaction of ZnO binding peptides (ZnO-BPs) and ZnO. The ZnO-BPs used are reported sequences G-12 (GLHVMHKVAPPR), GT-16 (GLHVMHKVAPPR-GGGC) and alanine mutants of G-12 (G-12A6, G-12A11 and G-12A12) whose interaction with ZnO during solution synthesis studies have been extensively investigated. The interactions of the ZnO-BPs with ZnO yielded biphasic isotherms comprising both an endo-thermic and an exothermic event. Qualitative differences were observed in the isothermal profiles of the different pep-tides and ZnO particles studied. Measured ΔG values were between -6 and -8.5 kcal/mol and high adsorption affinity val-ues indicated the occurrence of favourable ZnO-BP-ZnO interactions. ITC has great potential in its use to understand peptide-inorganic interactions and with continued development, the knowledge gained may be instrumental for simplifi-cation of selection processes of organic molecules for the advancement of material synthesis and design

Fluorescent Gold Nanoprobes for the Sensitive and Selective Detection for Hg2+

A simple, cost-effective yet rapid and sensitive sensor for on-site and real-time Hg2+ detection based on bovine serum albumin functionalized fluorescent gold nanoparticles as novel and environmentally friendly fluorescent probes was developed. Using this probe, aqueous Hg2+ can be detected at 0.1 nM in a facile way based on fluorescence quenching. This probe was also applied to determine the Hg2+ in the lake samples, and the results demonstrate low interference and high sensitivity

Micro/Nanoscale Parallel Patterning of Functional Biomolecules, Organic Fluorophores and Colloidal Nanocrystals

We describe the design and optimization of a reliable strategy that combines self-assembly and lithographic techniques, leading to very precise micro-/nanopositioning of biomolecules for the realization of micro- and nanoarrays of functional DNA and antibodies. Moreover, based on the covalent immobilization of stable and versatile SAMs of programmable chemical reactivity, this approach constitutes a general platform for the parallel site-specific deposition of a wide range of molecules such as organic fluorophores and water-soluble colloidal nanocrystals

Developing Biotemplated Data Storage: Room Temperature Biomineralization of L1<inf>0</inf> CoPt Magnetic Nanoparticles

L10 cobalt platinum can be used to record data at approximately sixfold higher densities than it is possible to on existing hard disks. Currently, fabricating L10 CoPt requires high temperatures (≈500 °C) and expensive equipment. One ecological alternative is to exploit biomolecules that template nanomaterials at ambient temperatures. Here, it is demonstrated that a dual affinity peptide (DAP) can be used to biotemplate L10 CoPt onto a surface at room temperature from an aqueous solution. One part of the peptide nucleates and controls the growth of CoPt nanoparticles from solution, and the other part binds to SiO2. A native silicon oxide surface is functionalized with a high loading of the DAP using microcontact printing. The DAP biotemplates a monolayer of uniformly sized and shaped nanoparticles when immobilized on the silicon surface. X-ray diffraction shows that the biotemplated nanoparticles have the L10 CoPt crystal structure, and magnetic measurements reveal stable, multiparticle zones of interaction, similar to those seen in perpendicular recording media. This is the first time that the L10 phase of CoPt has been formed without high temperature/vacuum treatment (e.g., annealing or sputtering) and offers a significant advancement toward developing environmentally friendly, biotemplated materials for use in data storage