Bifunctional Hexadentate Pyclen-Based Chelating Agent for Mild Radiofluorination in Aqueous Solution at Room Temperature with a Ga-F Ternary Complex.

Positron Emission Tomography (PET) is used in oncology for tumor diagnosis, commonly relying on fluorine-18 (F) emission detection. The conventional method of F incorporation on to probes by covalent bonding is harsh for sensitive biomolecules, which are nonetheless compounds of choice for the development of targeted probes. This study explores gallium-F (GaF) coordination, a milder alternative method occurring in aqueous media at the final stage of radiosyntheses.

Cyclic Oxothiomolybdates: Building Blocks for Cyclodextrin-Based Open Frameworks.

Desolvation processes, though common in self-assembled biological structures, are rarely evidenced and utilized in the design of crystalline architectures. In this study, we introduce a novel approach using the [MoSO(OH)(guest)] complex, formed by the self-condensation of four [Mo OS] fragments around a guest unit (MoOH or oxalate), as a chaotropic scaffold for crystallizing hybrid organic-inorganic systems with natural cyclodextrins. Our findings reveal that β-cyclodextrin (β-CD) facilitates the formation of host-guest complexes, while α-cyclodextrin (α-CD) induces the formation of a Kagome-type structure with significant voids.

Expanding the Reticular Chemistry Building Block Library toward Highly Connected Nets: Ultraporous MOFs Based on 18-Connected Ternary, Trigonal Prismatic Superpolyhedra.

The chemistry of metal-organic frameworks (MOFs) continues to expand rapidly, providing materials with diverse structures and properties. The reticular chemistry approach, where well-defined structural building blocks are combined together to form crystalline open framework solids, has greatly accelerated the discovery of new and important materials. However, its full potential toward the rational design of MOFs relies on the availability of highly connected building blocks because these greatly reduce the number of possible structures.

Cavity-Directed Synthesis of Labile Polyoxometalates for Catalysis in Confined Spaces.

The artificial microenvironments inside coordination cages have gained significant attention for performing enzyme-like catalytic reactions by facilitating the formation of labile and complex molecules through a "ship-in-a-bottle" approach. Despite many fascinating examples, this approach remains scarcely explored in the context of synthesizing metallic clusters such as polyoxometalates (POMs). The development of innovative approaches to control and influence the speciation of POMs in aqueous solutions would greatly advance their applicability and could ultimately lead to the formation of elusive clusters that cannot be synthesized by using traditional methods.

Cooperative Self-Assembly Process Involving Giant Toroidal Polyoxometalate as a Membrane Building Block in Nanoscale Vesicles.

The self-assembly of organic amphiphilic species into various aggregates such as spherical or elongated micelles and cylinders up to the formation of lyotropic hexagonal or lamellar phases results from cooperative processes orchestrated by the hydrophobic effect, while those involving ionic inorganic polynuclear entities and nonionic organic components are still intriguing. Herein, we report on the supramolecular behavior of giant toroidal molybdenum blue-type polyoxometalate, namely, the {Mo} species in the presence of n-octyl-β-glucoside (C8G1), widely used as a surfactant in biochemistry. Structural investigations were carried out using a set of complementary multiscale methods including single-crystal X-ray diffraction analysis supported by molecular modeling, small-angle X-ray scattering and cryo-TEM observations.

A Fluorinated BODIPY-Based Zirconium Metal-Organic Framework for Enhanced Photodynamic Therapy.

Photodynamic therapy (PDT), an emergent noninvasive cancer treatment, is largely dependent on the presence of efficient photosensitizers (PSs) and a sufficient oxygen supply. However, the therapeutic efficacy of PSs is greatly compromised by poor solubility, aggregation tendency, and oxygen depletion within solid tumors during PDT in hypoxic microenvironments. Despite the potential of PS-based metal-organic frameworks (MOFs), addressing hypoxia remains challenging.

Structure and Electronic Properties of Large Oligomeric Heterometallic 3d/Ce Polyoxometalates.

Merging the rich chemistry of Ce(IV) polyoxometalates (POMs) with that of 3d polyanions remains a challenge due to the strong competition between these highly oxophilic lanthanide cations and 3d metallic ions for coordination to lacunary molecular metal oxides. We report herein the characterization of an unprecedented water stable hexameric Ce/Co POM () made of two {(SiW)Ce} units connected to a {(SiW)Co(PO)} core. In addition, the pentameric Ce/Ni compound , where two {PWNiW} and a {PWNi} fragments are grafted on a {(PW)Ce} moiety, has been obtained.

A revision of the Chilean water penny genus Waterhouse, 1876 (Coleoptera, Psephenidae, Eubriinae), with description of a second species and two larval morphotypes, and notes on other Chilean Psephenidae.

The Chilean water penny genus Waterhouse, 1876 is revised, with descriptions and photographic illustrations of life stages including two larval morphotypes, the pupa of one morphotype, and adults of two species. The pupa of has not been reported previously. is described, and Ectopria (Chilectopria) grandis Pic, 1947, is proposed as a new synonym of Waterhouse, 1876, which is redescribed.

Rhithrops capensis gen. et sp. nov., a new aquatic dryopid beetle from the Western Cape of South Africa (Coleoptera: Dryopoidea: Dryopidae).

Rhithrops capensis gen. et sp. nov.

Ice crystallization under cryogenic cooling in lipid membrane nanoconfined geometry: Time-resolved structural dynamics.

Time-resolved structural investigations of crystallization of water in lipid/protein/salt mesophases at cryogenic temperatures are significant for comprehension of ice nanocrystal nucleation kinetics in lipid membranous systems and can lead to a better understanding of how to experimentally retard the ice formation that obstructs the protein crystal structure determination. Here, we present a time-resolved synchrotron microfocus X-ray diffraction (TR-XRD) study based on ∼40,000 frames that revealed the dynamics of water-to-ice crystallization in a lipid/protein/salt mesophase subjected to cryostream cooling at 100 K. The monoolein/hemoglobin/salt/water system was chosen as a model composition related to protein-loaded lipid cubic phases (LCP) broadly used for the crystallization of proteins.

Inorganic Drugs as a Tool for Protein Structure Solving and Studies on Conformational Changes.

Inorganic drugs are capable of tight interactions with proteins through coordination towards aminoacidic residues, and this feature is recognized as a key aspect for their pharmacological action. However, the "protein metalation process" is exploitable for solving the phase problem and structural resolution. In fact, the use of inorganic drugs bearing specific metal centers and ligands capable to drive the binding towards the desired portions of the protein target could represent a very intriguing and fruitful strategy.

Structural Variety of Niobium(V) Polyoxo Clusters Obtained from the Reaction with Aromatic Monocarboxylic Acids: Isolation of {Nb O}, {Nb O } and {Nb O } Cores.

The reactivity of aryl monocarboxylic acids (benzoic, 1- or 2-naphtoic, 4'-methylbiphenyl-4-carboxylic, and anthracene-9-carboxylic acids) as complexing agents for the ethoxide niobium(V) (Nb(OEt) precursor has been investigated. A total of eight coordination complexes were isolated with distinct niobium(V) nuclearities as well as carboxylate complexation states. The use of benzoic acid gives a tetranuclear core Nb (μ -O) (L) (OEt) ] (L=benzoate (1)) with four Nb-(μ -O)-Nb linkages in a square plane configuration.

The crystal structure of iC3b-CR3 αI reveals a modular recognition of the main opsonin iC3b by the CR3 integrin receptor.

Complement activation on cell surfaces leads to the massive deposition of C3b, iC3b, and C3dg, the main complement opsonins. Recognition of iC3b by complement receptor type 3 (CR3) fosters pathogen opsonophagocytosis by macrophages and the stimulation of adaptive immunity by complement-opsonized antigens. Here, we present the crystallographic structure of the complex between human iC3b and the von Willebrand A inserted domain of the α chain of CR3 (αI).

Chaotropic Effect as an Assembly Motif to Construct Supramolecular Cyclodextrin-Polyoxometalate-Based Frameworks.

In aqueous solution, low-charged polyoxometalates (POMs) exhibit remarkable self-assembly properties with nonionic organic matter that have been recently used to develop groundbreaking advances in host-guest chemistry, as well as in soft matter science. Herein, we exploit the affinity between a chaotropic POM and native cyclodextrins (α-, β-, and γ-CD) to enhance the structural and functional diversity of cyclodextrin-based open frameworks. First, we reveal that the Anderson-Evans type polyoxometalate [AlMoO(OH)] represents an efficient inorganic scaffold to design open hybrid frameworks built from infinite cyclodextrin channels connected through the disk-shaped POM.

A review of the Larainae of Australia with description of seven new species and the new genus (Coleoptera, Byrrhoidea, Elmidae).

The three genera and four species of Larainae (Elmidae) previously described from Australia are reviewed, and one new genus and seven new species are described: , , , , , , and A lectotype is designated for (Carter & Zeck), and the first new collection records of the species are reported since its description in 1932. The occurrence in Australia of Satô, described from Papua New Guinea, is reported. A key to the species, photographic images of the external morphology and male genitalia, distribution maps, and habitat and behavioral information, when known, are provided for all twelve species of Australian Larainae.

Host-Guest Complexation Between Cyclodextrins and Hybrid Hexavanadates: What are the Driving Forces?

Host-guest complexes between native cyclodextrins (α-, β- and γ-CD) and hybrid Lindqvist-type polyoxovanadates (POVs) [V O ((OCH ) C-R) ] with R = CH CH , NO , CH OH and NH(BOC) (BOC = N-tert-butoxycarbonyl) were studied in aqueous solution. Six crystal structures determined by single-crystal X-ray diffraction analysis revealed the nature of the functional R group strongly influences the host-guest conformation and also the crystal packing. In all systems isolated in the solid-state, the organic groups R are embedded within the cyclodextrin cavities, involving only a few weak supramolecular contacts.

"Host in Host" Supramolecular Core-Shell Type Systems Based on Giant Ring-Shaped Polyoxometalates.

Herein, we show how the chaotropic effect arising from reduced molybdate ions in acidified aqueous solution is able to amplify drastically weak supramolecular interactions. Time-resolved Small Angle X-ray Scattering (SAXS) analysis suggests that molybdenum-blue oligomeric species form huge aggregates in the presence of γ-cyclodextrin (γ-CD) which results in the fast formation of nanoscopic {Mo }-based host-guest species, while X-ray diffraction analysis reveals that the ending-point of the scenario results in an unprecedented three-component well-ordered core-shell-like motif. A similar arrangement was found by using preformed hexarhenium chalcogenide-type cluster [Re Te (CN) ] as exogenous guest.

Hiding in plain sight: rediscovery and review of Parygrus Erichson, 1847, with description of five new species from the Neotropics (Coleoptera: Byrrhoidea: Dryopidae).

The history and original concept of Parygrus Erichson, 1847, is reviewed, the genus is redescribed, and the status of the type species, P. erichsoni Waterhouse, 1876, is clarified. The four original species are reviewed, with photographs provided for the type specimens of P.

Using Phaser and ensembles to improve the performance of SIMBAD.

The conventional approach to search-model identification in molecular replacement (MR) is to screen a database of known structures using the target sequence. However, this strategy is not always effective, for example when the relationship between sequence and structural similarity fails or when the crystal contents are not those expected. An alternative approach is to identify suitable search models directly from the experimental data.

An Institutional Review: Which Metrics Correlate With a Successful United States Medical Licensing Examination Step 1 Score?

Purpose: Since the introduction of the Comprehensive Basic Science Examination (CBSE) as an entrance examination in 2012, no studies have been performed correlating its relationship with passing rates on United States Medical Licensing Examination (USMLE) Step 1 in dental students. This study was designed to determine the impact of the CBSE score, dental grade point average (GPA), and undergraduate GPA on USMLE Step 1 performance and develop a CBSE cutoff score that correlates with a passing USMLE score.

Materials And Methods: A single-blinded, retrospective, cross-sectional study was designed.

Engineering Structural Dynamics of Zirconium Metal-Organic Frameworks Based on Natural C4 Linkers.

Engineering the structural flexibility of metal-organic framework (MOF) materials for separation-related applications remains a great challenge. We present here a strategy of mixing rigid and soft linkers in a MOF structure to achieve tunable structural flexibility, as exemplified in a series of stable isostructural Zr-MOFs built with natural C4 linkers (fumaric acid, succinic acid, and malic acid). As shown by the differences in linker bond stretching and bending freedom, these MOFs display distinct responsive dynamics to external stimuli, namely, changes in temperature or guest molecule type.

Redox-Active 1D Coordination Polymers of Iron-Sulfur Clusters.

Here we describe the combination of an archetypal redox-active metal sulfide cluster, FeS, with an organic linker, 1,4-benzenedithiolate, to prepare coordination polymers containing infinite chains of FeS clusters. The crystal structures of two solid materials have been solved from synchrotron X-ray powder diffraction data using simulated annealing and refined by a least-squares Rietveld refinement procedure. The electronic properties of these chains have also been characterized by UV-visible and Mössbauer spectroscopies.