Incorporation of Tb and Gd improves the diagnostic functionality of magnetotactic bacteria.

Magnetotactic bacteria are envisaged as potential theranostic agents. Their internal magnetic compass, chemical environment specificity and natural motility enable these microorganisms to behave as nanorobots, as they can be tracked and guided towards specific regions in the body and activated to generate a therapeutic response. Here we provide additional diagnostic functionalities to magnetotactic bacteria Magnetospirillum gryphiswaldense MSR-1 while retaining their intrinsic capabilities. These additional functionalities are achieved by incorporating Tb or Gd in the bacteria by culturing them in Tb/Gd supplemented media. The incorporation of Tb provides luminescence properties, enabling potential applications of bacteria as biomarkers. The incorporation of Gd turns bacteria into dual contrast agents for magnetic resonance imaging, since Gd adds T1 contrast to the existing T2 contrast of unmodified bacteria. Given their potential clinical applications, the diagnostic ability of the modified MSR-1 has been successfully tested in vitro in two cell models, confirming their suitability as fluorescent markers (Tb-MSR-1) and dual contrast agents for MRI (Gd-MSR-1).

Collective magnetotaxis of microbial holobionts is optimized by the three-dimensional organization and magnetic properties of ectosymbionts.

Over the last few decades, symbiosis and the concept of holobiont-a host entity with a population of symbionts-have gained a central role in our understanding of life functioning and diversification. Regardless of the type of partner interactions, understanding how the biophysical properties of each individual symbiont and their assembly may generate collective behaviors at the holobiont scale remains a fundamental challenge. This is particularly intriguing in the case of the newly discovered magnetotactic holobionts (MHB) whose motility relies on a collective magnetotaxis (i.e., a magnetic field-assisted motility guided by a chemoaerotaxis system). This complex behavior raises many questions regarding how magnetic properties of symbionts determine holobiont magnetism and motility. Here, a suite of light-, electron- and X-ray-based microscopy techniques [including X-ray magnetic circular dichroism (XMCD)] reveals that symbionts optimize the motility, the ultrastructure, and the magnetic properties of MHBs from the microscale to the nanoscale. In the case of these magnetic symbionts, the magnetic moment transferred to the host cell is in excess (102 to 103 times stronger than free-living magnetotactic bacteria), well above the threshold for the host cell to gain a magnetotactic advantage. The surface organization of symbionts is explicitly presented herein, depicting bacterial membrane structures that ensure longitudinal alignment of cells. Magnetic dipole and nanocrystalline orientations of magnetosomes were also shown to be consistently oriented in the longitudinal direction, maximizing the magnetic moment of each symbiont. With an excessive magnetic moment given to the host cell, the benefit provided by magnetosome biomineralization beyond magnetotaxis can be questioned.

Crystal-Chemical and Biological Controls of Elemental Incorporation into Magnetite Nanocrystals.

Magnetite nanoparticles possess numerous fundamental, biomedical, and industrial applications, many of which depend on tuning the magnetic properties. This is often achieved by the incorporation of trace and minor elements into the magnetite lattice. Such incorporation was shown to depend strongly on the magnetite formation pathway (i.e., abiotic vs biological), but the mechanisms controlling element partitioning between magnetite and its surrounding precipitation solution remain to be elucidated. Here, we used a combination of theoretical modeling (lattice and crystal field theories) and experimental evidence (high-resolution inductively coupled plasma-mass spectrometry and X-ray absorption spectroscopy) to demonstrate that element incorporation into abiotic magnetite nanoparticles is controlled principally by cation size and valence. Elements from the first series of transition metals (Cr to Zn) constituted exceptions to this finding, as their incorporation appeared to be also controlled by the energy levels of their unfilled 3d orbitals, in line with crystal field mechanisms. We finally show that element incorporation into biological magnetite nanoparticles produced by magnetotactic bacteria (MTB) cannot be explained by crystal-chemical parameters alone, which points to the biological control exerted by the bacteria over the element transfer between the MTB growth medium and the intracellular environment. This screening effect generates biological magnetite with a purer chemical composition in comparison to the abiotic materials formed in a solution of similar composition. Our work establishes a theoretical framework for understanding the crystal-chemical and biological controls of trace and minor cation incorporation into magnetite, thereby providing predictive methods to tailor the composition of magnetite nanoparticles for improved control over magnetic properties.

An open-source automated magnetic optical density meter for analysis of suspensions of magnetic cells and particles.

We present a spectrophotometer (optical density meter) combined with electromagnets dedicated to the analysis of suspensions of magnetotactic bacteria. The instrument can also be applied to suspensions of other magnetic cells and magnetic particles. We have ensured that our system, called MagOD, can be easily reproduced by providing the source of the 3D prints for the housing, electronic designs, circuit board layouts, and microcontroller software. We compare the performance of our system to existing adapted commercial spectrophotometers. In addition, we demonstrate its use by analyzing the absorbance of magnetotactic bacteria as a function of their orientation with respect to the light path and their speed of reorientation after the field has been rotated by 90°. We continuously monitored the development of a culture of magnetotactic bacteria over a period of 5 days and measured the development of their velocity distribution over a period of one hour. Even though this dedicated spectrophotometer is relatively simple to construct and cost-effective, a range of magnetic field-dependent parameters can be extracted from suspensions of magnetotactic bacteria. Therefore, this instrument will help the magnetotactic research community to understand and apply this intriguing micro-organism.

Periplasmic Bacterial Biomineralization of Copper Sulfide Nanoparticles.

Metal sulfides are a common group of extracellular bacterial biominerals. However, only a few cases of intracellular biomineralization are reported in this group, mostly limited to greigite (Fe3 S4 ) in magnetotactic bacteria. Here, a previously unknown periplasmic biomineralization of copper sulfide produced by the magnetotactic bacterium Desulfamplus magnetovallimortis strain BW-1, a species known to mineralize greigite (Fe3 S4 ) and magnetite (Fe3 O4 ) in the cytoplasm is reported. BW-1 produces hundreds of spherical nanoparticles, composed of 1-2 nm substructures of a poorly crystalline hexagonal copper sulfide structure that remains in a thermodynamically unstable state. The particles appear to be surrounded by an organic matrix as found from staining and electron microscopy inspection. Differential proteomics suggests that periplasmic proteins, such as a DegP-like protein and a heavy metal-binding protein, could be involved in this biomineralization process. The unexpected periplasmic formation of copper sulfide nanoparticles in BW-1 reveals previously unknown possibilities for intracellular biomineralization that involves intriguing biological control and holds promise for biological metal recovery in times of copper shortage.

Catalytic and photoresponsive BiZ/CuxS heterojunctions with surface vacancies for the treatment of multidrug-resistant clinical biofilm-associated infections.

We report a one-pot facile synthesis of highly photoresponsive bovine serum albumin (BSA) templated bismuth-copper sulfide nanocomposites (BSA-BiZ/CuxS NCs, where BiZ represents in situ formed Bi2S3 and bismuth oxysulfides (BOS)). As-formed surface vacancies and BiZ/CuxS heterojunctions impart superior catalytic, photodynamic and photothermal properties. Upon near-infrared (NIR) irradiation, the BSA-BiZ/CuxS NCs exhibit broad-spectrum antibacterial activity, not only against standard multidrug-resistant (MDR) bacterial strains but also against clinically isolated MDR bacteria and their associated biofilms. The minimum inhibitory concentration of BSA-BiZ/CuxS NCs is 14-fold lower than that of BSA-CuxS NCs because their multiple heterojunctions and vacancies facilitated an amplified phototherapeutic response. As-prepared BSA-BiZ/CuxS NCs exhibited substantial biofilm inhibition (90%) and eradication (>75%) efficiency under NIR irradiation. Furthermore, MRSA-infected diabetic mice were immensely treated with BSA-BiZ/CuxS NCs coupled with NIR irradiation by destroying the mature biofilm on the wound site, which accelerated the wound healing process via collagen synthesis and epithelialization. We demonstrate that BSA-BiZ/CuxS NCs with superior antimicrobial activity and high biocompatibility hold great potential as an effective photosensitive agent for the treatment of biofilm-associated infections.

Wettability of Magnetite Nanoparticles Guides Growth from Stabilized Amorphous Ferrihydrite.

Crystal formation via amorphous precursors is a long-sought-after gateway to engineer nanoparticles with well-controlled size and morphology. Biomineralizing organisms, like magnetotactic bacteria, follow such a nonclassical crystallization pathway to produce magnetite nanoparticles with sophistication unmatched by synthetic efforts at ambient conditions. Here, using in situ small-angle X-ray scattering, we demonstrate how the addition of poly(arginine) in the synthetic formation of magnetite nanoparticles induces a biomineralization-reminiscent pathway. The addition of poly(arginine) stabilizes an amorphous ferrihydrite precursor, shifting the magnetite formation pathway from thermodynamic to kinetic control. Altering the energetic landscape of magnetite formation by catalyzing the pH-dependent precursor attachment, we tune magnetite nanoparticle size continuously, exceeding sizes observed in magnetotactic bacteria. This mechanistic shift we uncover here further allows for crystal morphology control by adjusting the pH-dependent interfacial interaction between liquidlike ferrihydrite and nascent magnetite nanoparticles, establishing a new strategy to control nanoparticle morphology. Synthesizing compact single crystals at wetting conditions and unique semicontinuous single-crystalline nanoparticles at dewetting conditions in combination with an improved control over magnetite crystallite size, we demonstrate the versatility of bio-inspired, kinetically controlled nanoparticle formation pathways.

Interactions between Ultrastable Na4Ag44(SR)30 Nanoclusters and Coordinating Solvents: Uncovering the Atomic-Scale Mechanism.

Recently, silver nanoclusters have garnered considerable attention after the high-yield synthesis and crystallization of a thiolate-protected silver nanocluster, Na4Ag44(SR)30 (SR, protecting thiolate ligand). One intriguing feature of Na4Ag44(SR)30 is its outstanding stability and resistance to chemical reactions, in striking difference from other silver nanostructures whose susceptibility to oxidation (tarnishing) has been commonly observed and thus limits their applications in nanotechnology. Herein, we report the mechanism on the ultrahigh stability of Na4Ag44(SR)30 by uncovering how coordinating solvents interact with the Na4Ag44(SR)30 nanocluster at the atomic scale. Through synchrotron X-ray experiments and theoretical calculations, it was found that strongly coordinating aprotic solvents interact with surface Ag atoms, particularly between ligand bundles, which compresses the Ag core and relaxes surface metal-ligand interactions. Furthermore, water was used as a cosolvent to demonstrate that semiaqueous conditions play an important role in protecting exposed surface regions and can further influence the local structure of the silver nanocluster itself. Notably, under semiaqueous conditions, aprotic coordinating solvent molecules preferentially remain on the metal surface while water molecules interact with ligands, and ligand bundling persisted across the varied solvation conditions. This work offers an atomic level mechanism on the ultrahigh stability of the Na4Ag44(SR)30 nanoclusters from the nanocluster-coordinating solvent interaction perspective, and implies that nanocluster-solvent interactions should be carefully considered moving forward for silver nanoclusters, as they can influence the electronic/chemical properties of the nanocluster as well as the surface accessibility of small molecules for potential catalytic and biomedical applications.

Doxorubicin-loaded polyphosphate glass microspheres for transarterial chemoembolization.

The standard of care for intermediate stage hepatocellular carcinoma is transarterial chemoembolization (TACE). Drug-eluting bead TACE (DEB-TACE) has emerged as a leading form of TACE, as it uses highly calibrated microspheres to deliver consistent embolization and controlled drug release to the tumor microenvironment. We report here on doxorubicin (DOX)-loaded polyphosphate glass microspheres (PGM) as a novel resorbable, radiopaque, preloaded DEB-TACE platform. Coacervate composed of polyphosphate chains complexed with Ba2+ , Ca2+ , and Cu2+ can be loaded with DOX prior to PGM synthesis, with PGM production achieved using a water-in-oil emulsion technique at room temperature yielding highly spherical particles in clinically relevant size fractions. In vitro, DOX release was found to be linear, pH dependent, and in accordance with Type II non-Fickian transport. PGM degradation was characterized by an initial burst release of degradation products over 7 days, followed by a plateau in mass loss at approximately 75% over a period of several weeks. in vitro studies indicate that PGM degradation products, namely Cu2+ , are cytotoxic and may interact with eluted DOX to impair its pharmacological activity. With additional compositional considerations, this approach may prove promising for DEB-TACE applications.

Molecular-Scale Ligand Effects in Small Gold-Thiolate Nanoclusters.

Because of the small size and large surface area of thiolate-protected Au nanoclusters (NCs), the protecting ligands are expected to play a substantial role in modulating the structure and properties, particularly in the solution phase. However, little is known on how thiolate ligands explicitly modulate the structural properties of the NCs at atomic level, even though this information is critical for predicting the performance of Au NCs in application settings including as a catalyst interacting with small molecules and as a sensor interacting with biomolecular systems. Here, we report a combined experimental and theoretical study, using synchrotron X-ray spectroscopy and quantum mechanics/molecular mechanics simulations, that investigates how the protecting ligands impact the structure and properties of small Au18(SR)14 NCs. Two representative ligand types, smaller aliphatic cyclohexanethiolate and larger hydrophilic glutathione, are selected, and their structures are followed experimentally in both solid and solution phases. It was found that cyclohexanethiolate ligands are significantly perturbed by toluene solvent molecules, resulting in structural changes that cause disorder on the surface of Au18(SR)14 NCs. In particular, large surface cavities in the ligand shell are created by interactions between toluene and cyclohexanethiolate. The appearance of these small molecule-accessible sites on the  NC surface demonstrates the ability of Au NCs to act as a catalyst for organic phase reactions. In contrast, glutathione ligands encapsulate the Au NC core via intermolecular interactions, minimizing structural changes caused by interactions with water molecules. The much better protection from glutathione ligands imparts a rigidified surface and ligand structure, making the NCs desirable for biomedical applications due to the high stability and also offering a structural-based explanation for the enhanced photoluminescence often reported for glutathione-protected Au NCs.

Distinct Short-Range Order Is Inherent to Small Amorphous Calcium Carbonate Clusters (<2†nm).

Amorphous intermediate phases are vital precursors in the crystallization of many biogenic minerals. While inherent short-range orders have been found in amorphous calcium carbonates (ACCs) relating to different crystalline forms, it has never been clarified experimentally whether such orders already exist in very small clusters less than 2 nm in size. Here, we studied the stability and structure of 10,12-pentacosadiynoic acid (PCDA) protected ACC clusters with a core size of ca. 1.4 nm consisting of only seven CaCO3 units. Ligand concentration and structure are shown to be key factors in stabilizing the ACC clusters. More importantly, even in such small CaCO3 entities, a proto-calcite short-range order can be identified but with a relatively high degree of disorder that arises from the very small size of the CaCO3 core. Our findings support the notion of a structural link between prenucleation clusters, amorphous intermediates, and final crystalline polymorphs, which appears central to the understanding of polymorph selection.

Water as the Key to Proto-Aragonite Amorphous CaCO3.

Temperature and pH value can affect the short-range order of proto-structured and additive-free amorphous calcium carbonates (ACCs). Whereas a distinct change occurs in proto-vaterite (pv) ACC above 45 °C at pH 9.80, proto-calcite (pc) ACC (pH 8.75) is unaffected within the investigated range of temperatures (7-65 °C). IR and NMR spectroscopic studies together with EXAFS analysis showed that the temperature-induced change is related to the formation of proto-aragonite (pa) ACC. The data strongly suggest that the binding of water molecules induces dipole moments across the carbonate ions in pa-ACC as in aragonite, where the dipole moments are due to the symmetry of the crystal structure. Altogether, a (pseudo-)phase diagram of the CaCO3 polyamorphism in which water plays a key role can be formulated based on variables of state, such as the temperature, and solution parameters, such as the pH value.

Photochemical route for synthesizing atomically dispersed palladium catalysts.

Atomically dispersed noble metal catalysts often exhibit high catalytic performances, but the metal loading density must be kept low (usually below 0.5%) to avoid the formation of metal nanoparticles through sintering. We report a photochemical strategy to fabricate a stable atomically dispersed palladium-titanium oxide catalyst (Pd1/TiO2) on ethylene glycolate (EG)-stabilized ultrathin TiO2 nanosheets containing Pd up to 1.5%. The Pd1/TiO2 catalyst exhibited high catalytic activity in hydrogenation of C=C bonds, exceeding that of surface Pd atoms on commercial Pd catalysts by a factor of 9. No decay in the activity was observed for 20 cycles. More important, the Pd1/TiO2-EG system could activate H2 in a heterolytic pathway, leading to a catalytic enhancement in hydrogenation of aldehydes by a factor of more than 55.

A Segregated, Partially Oxidized, and Compact Ag10 Cluster within an Encapsulating DNA Host.

Silver clusters develop within DNA strands and become optical chromophores with diverse electronic spectra and wide-ranging emission intensities. These studies consider a specific cluster that absorbs at 400 nm, has low emission, and exclusively develops with single-stranded oligonucleotides. It is also a chameleon-like chromophore that can be transformed into different highly emissive fluorophores. We describe four characteristics of this species and conclude that it is highly oxidized yet also metallic. One, the cluster size was determined via electrospray ionization mass spectrometry. A common silver mass is measured with different oligonucleotides and thereby supports a Ag10 cluster. Two, the cluster charge was determined by mass spectrometry and Ag L3-edge X-ray absorption near-edge structure spectroscopy. Respectively, the conjugate mass and the integrated white-line intensity support a partially oxidized cluster with a +6 and +6.5 charge, respectively. Three, the cluster chirality was gauged by circular dichroism spectroscopy. This chirality changes with the length and sequence of its DNA hosts, and these studies identified a dispersed binding site with ∼20 nucleobases. Four, the structure of this complex was investigated via Ag K-edge extended X-ray absorption fine structure spectroscopy. A multishell fitting analysis identified three unique scattering environments with corresponding bond lengths, coordination numbers, and Debye-Waller factors for each. Collectively, these findings support the following conclusion: a Ag10(+6) cluster develops within a 20-nucleobase DNA binding site, and this complex segregates into a compact, metal-like silver core that weakly links to an encapsulating silver-DNA shell. We consider different models that account for silver-silver coordination within the core.

Description and Role of Bimetallic Prenucleation Species in the Formation of Small Nanoparticle Alloys.

We report the identification, description, and role of multinuclear metal-thiolate complexes in aqueous Au-Cu nanoparticle syntheses. The structure of these species was characterized by nuclear magnetic resonance spectroscopy, mass spectrometry, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy techniques. The observed structures were found to be in good agreement with thermodynamic growth trends predicted by first-principles calculations. The presence of metal-thiolate complexes is then shown to be critical for the formation of alloyed Au-Cu architectures in the small nanoparticle regime (diameter ∼2 nm). In the absence of mixed metal-thiolate precursors, nanoparticles form with a Cu-S shell and a Au-rich interior. Taken together, these results demonstrate that prenucleation species, which are discrete molecular precursors distinct from both initial reagents and final particle products, may provide an important new synthetic route to control final metal nanoparticle composition and composition architectures.

Energy Migration Upconversion in Manganese(II)-Doped Nanoparticles.

We report the synthesis and characterization of cubic NaGdF4:Yb/Tm@NaGdF4:Mn core-shell structures. By taking advantage of energy transfer through Yb→Tm→Gd→Mn in these core-shell nanoparticles, we have realized upconversion emission of Mn(2+) at room temperature in lanthanide tetrafluoride based host lattices. The upconverted Mn(2+) emission, enabled by trapping the excitation energy through a Gd(3+) lattice, was validated by the observation of a decreased lifetime from 941 to 532 µs in the emission of Gd(3+) at 310 nm ((6)P(7/2)→(8)S(7/2)). This multiphoton upconversion process can be further enhanced under pulsed laser excitation at high power densities. Both experimental and theoretical studies provide evidence for Mn(2+) doping in the lanthanide-based host lattice arising from the formation of F(-) vacancies around Mn(2+) ions to maintain charge neutrality in the shell layer.

Identification of a highly luminescent Au22(SG)18 nanocluster.

The luminescence property of thiolated gold nanoclusters (Au NCs) is thought to involve the Au(I)-thiolate motifs on the NC surface; however, this hypothesis remains largely unexplored because of the lack of precise molecular composition and structural information of highly luminescent Au NCs. Here we report a new red-emitting thiolated Au NC, which has a precise molecular formula of Au22(SR)18 and exhibits intense luminescence. Interestingly, this new Au22(SR)18 species shows distinctively different absorption and emission features from the previously reported Au22(SR)16, Au22(SR)17, and Au25(SR)18. In stark contrast, Au22(SR)18 luminesces intensely at ∼665 nm with a high quantum yield of ∼8%, while the other three Au NCs show very weak luminescence. Our results indicate that the luminescence of Au22(SR)18 originates from the long Au(I)-thiolate motifs on the NC surface via the aggregation-induced emission pathway. Structure prediction by density functional theory suggests that Au22(SR)18 has two RS-[Au-SR]3 and two RS-[Au-SR]4 motifs, interlocked and capping on a prolate Au8 core. This predicted structure is further verified experimentally by Au L3-edge X-ray absorption fine structure analysis.

Germanate with three-dimensional 12 × 12 × 11-ring channels solved by X-ray powder diffraction with charge-flipping algorithm.

A new open-framework germanate, denoted as GeO-JU90, was prepared by the hydrothermal synthesis method using 1,5-bis(methylpyrrolidinium)pentane dihydroxide as the organic structure-directing agent (SDA). The structure of GeO-JU90 was determined from synchrotron X-ray powder diffraction (XRPD) data using the charge-flipping algorithm. It revealed a complicated framework structure containing 11 Ge atoms in the asymmetric unit. The framework is built of 7-connected Ge7 clusters and additional tetrahedral GeO3(OH) units forming a new three-dimensional interrupted framework with interesting 12 × 12 × 11-ring intersecting channels. The Ge K-edge extended X-ray absorption fine structure (EXAFS) analysis was performed to provide the local structural information around Ge atoms, giving rise to a first-shell contribution from about 4.2(2) O atoms at the average distance of 1.750(8) Å. The guest species in the channels were subsequently determined by the simulated annealing method from XRPD data combining with other characterization techniques, e.g., (13)C NMR spectroscopy, infrared spectroscopy (FTIR), compositional analyses, and thermogravimetric analysis (TGA). Crystallographic data |(C15N2H32)(NH4)|[Ge11O21.5(OH)4], orthorhombic Ama2 (No. 40), a = 37.82959 Å, b = 15.24373 Å, c = 12.83659 Å, and Z = 8.

Unique Bonding Properties of the Au36(SR)24 Nanocluster with FCC-Like Core.

The recent discovery on the total structure of Au36(SR)24, which was converted from biicosahedral Au38(SR)24, represents a surprising finding of a face-centered cubic (FCC)-like core structure in small gold-thiolate nanoclusters. Prior to this finding, the FCC feature was only expected for larger (nano)crystalline gold. Herein, we report results on the unique bonding properties of Au36(SR)24 that are associated with its FCC-like core structure. Temperature-dependent X-ray absorption spectroscopy (XAS) measurements at the Au L3-edge, in association with ab initio calculations, show that the local structure and electronic behavior of Au36(SR)24 are of more molecule-like nature, whereas its icosahedral counterparts such as Au38(SR)24 and Au25(SR)18 are more metal-like. Moreover, site-specific S K-edge XAS studies indicate that the bridging motif for Au36(SR)24 has different bonding behavior from the staple motif from Au38(SR)24. Our findings highlight the important role of "pseudo"-Au4 units within the FCC-like Au28 core in interpreting the bonding properties of Au36(SR)24 and suggest that FCC-like structure in gold thiolate nanoclusters should be treated differently from its bulk counterpart.