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At least 1,279 records · Page 71

Transport of metformin metabolites by guanidinium exporters of the small multidrug resistance family

Proteins from the small multidrug resistance (SMR) family are frequently associated with horizontally transferred multidrug resistance gene arrays found in bacteria from wastewater and the human-adjacent biosphere. Recent studies suggest that a subset of SMR transporters might participate in the metabolism of the common pharmaceutical metformin by bacterial consortia. Here, we show that both genomic and plasmid-associated transporters of the SMRGdx functional subtype export byproducts of microbial metformin metabolism, with particularly high export efficiency for guanylurea. We use solid-supported membrane electrophysiology to evaluate the transport kinetics for guanylurea and native substrate guanidinium by four representative SMRGdx homologs. Using an internal reference to normalize independent electrophysiology experiments, we show that transport rates are comparable for genomic and plasmid-associated SMRGdx homologs, and using a proteoliposome-based transport assay, we show that 2 proton:1 substrate transport stoichiometry is maintained. Additional characterization of guanidinium and guanylurea export properties focuses on the structurally characterized homolog, Gdx-Clo, for which we examined the pH dependence and thermodynamics of substrate binding and solved an x-ray crystal structure with guanylurea bound. Together, these experiments contribute in two main ways. By providing the first detailed kinetic examination of the structurally characterized SMRGdx homolog Gdx-Clo, they provide a functional framework that will inform future mechanistic studies of this model transport protein. Second, this study casts light on a potential role for SMRGdx transporters in microbial handling of metformin and its microbial metabolic byproducts, providing insight into how native transport physiologies are co-opted to contend with new selective pressures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of a preQ1-I riboswitch in effector-free and bound states reveals a metabolite-programmed nucleobase-stacking spine that controls gene regulation

Abstract Riboswitches are structured RNA motifs that recognize metabolites to alter the conformations of downstream sequences, leading to gene regulation. To investigate this molecular framework, we determined crystal structures of a preQ1-I riboswitch in effector-free and bound states at 2.00 Å and 2.65 Å-resolution. Both pseudoknots exhibited the elusive L2 loop, which displayed distinct conformations. Conversely, the Shine-Dalgarno sequence (SDS) in the S2 helix of each structure remained unbroken. The expectation that the effector-free state should expose the SDS prompted us to conduct solution experiments to delineate environmental changes to specific nucleobases in response to preQ1. We then used nudged elastic band computational methods to derive conformational-change pathways linking the crystallographically-determined effector-free and bound-state structures. Pathways featured: (i) unstacking and unpairing of L2 and S2 nucleobases without preQ1—exposing the SDS for translation and (ii) stacking and pairing L2 and S2 nucleobases with preQ1—sequestering the SDS. Our results reveal how preQ1 binding reorganizes L2 into a nucleobase-stacking spine that sequesters the SDS, linking effector recognition to biological function. The generality of stacking spines as conduits for effector-dependent, interdomain communication is discussed in light of their existence in adenine riboswitches, as well as the turnip yellow mosaic virus ribosome sensor.

59 BASIC BIOLOGICAL SCIENCES↗

Complex magnetic order in the decorated spin-chain system Rb 2 Mn 3 ( MoO 4 ) 3 ( OH ) 2

The macroscopic magnetic properties and microscopic magnetic structure of Rb 2 Mn 3 (MoO 4 ) 3 (OH) 2 (space group Pn ma) are investigated by magnetization, heat capacity, and single-crystal neutron diffraction measurements. The compound's crystal structure contains bond-alternating [Mn 3 O 11 ] ∞ chains along the b axis, formed by isosceles triangles of Mn ions occupying two crystallographically nonequivalent sites (the Mn1 site on the base and Mn2 site on the vertex). These chains are only weakly linked to each other by nonmagnetic oxyanions. Both superconducting quantum interference device magnetometry and neutron diffraction experiments show two successive magnetic transitions as a function of temperature. On cooling, it transitions from a paramagnetic phase into an incommensurate phase below 4.5 K with a magnetic wave vector near k 1 = ( 0 , 0.46 , 0 ). An additional commensurate antiferromagnetically ordered component arises with k 2 = ( 0, 0, 0), forming a complex magnetic structure below 3.5 K with two different propagation vectors of different stars. On further cooling, the incommensurate wave vector undergoes a lock-in transition below 2.3 K. The experimental results suggest that the magnetic superspace group is Pnma. 1' (0b0) s0ss for the single- k incommensurate phase and is Pn' m a ( 0 b 0 ) 00 s for the two- k magnetic phase. We propose a simplified magnetic structure model taking into account the major ordered contributions, where the commensurate k 2 defines the ordering of the c-axis component of the Mn1 magnetic moment, while the incommensurate k 1 describes the ordering of the ab -plane components of both Mn1 and Mn2 moments into elliptical cycloids.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Synthesis and characterization of the novel breathing pyrochlore compound Ba 3 ⁢Tm 2⁢ Zn 5⁢ O 11

In this study, a novel material from the rare-earth based breathing pyrochlore family, Ba 3 ⁢Tm 2 ⁢Zn 5 ⁢O 11 , was successfully synthesized. Powder x-ray diffraction and high-resolution powder neutron diffraction confirmed phase purity and the $F\bar4$3⁢𝑚 breathing pyrochlore crystal structure, while thermogravimetric analysis revealed incongruent melting behavior compared to its counterpart, Ba 3 ⁢Yb 2⁢ Zn 5⁢ O 11 . High-quality single crystals of Ba 3 ⁢Tm 2 ⁢Zn 5 ⁢O 11 were grown using the traveling solvent floating zone technique and assessed using Laue x-ray diffraction and single crystal x-ray diffraction. Further, thermodynamic characterization indicated paramagnetic behavior down to 0.05 K, and inelastic neutron scattering measurements identified distinct dispersionless crystal electric field energy bands, with the fitted crystal electric field model predicting a single-ion singlet ground state and an energy gap of ∼9 meV separating it from the first excited (singlet) state. Additional low-energy excitation studies on single crystals revealed dispersionless bands at 0.8 and 1 meV. Computed phonon dispersions from first-principles calculations ruled out phonons as the origin of these modes, further illustrating the puzzling and unique properties of Ba 3 ⁢Tm⁢ 2 Zn 5 ⁢O 11 .

36 MATERIALS SCIENCE↗

Encapsulation and retention of 225 Ac, 223 Ra, 227 Th, and decay daughters in zircon-type gadolinium vanadate nanoparticles

Abstract Unwanted targeting of healthy organs caused by the relocation of radionuclides from the target site has been one of the limiting factors in the widespread application of targeted alpha therapy in patient regimens. GdVO 4 nanoparticles (NPs) were developed as platforms to encapsulate α -emitting radionuclides 223 Ra, 225 Ac, and 227 Th, and retain their decay daughters at the target site. Polycrystalline GdVO 4 NPs with different morphologies and a zircon-type tetragonal crystal structure were obtained by precipitation of GdCl 3 and Na 3 VO 4 in aqueous media at room temperature. The ability of GdVO 4 crystals to host multivalent ions was initially assessed using La, Cs, Bi, Ba, and Pb as surrogates of the radionuclides under investigation. A decrease in Ba encapsulation was obtained after increasing the concentration of surrogate ions, whereas the encapsulation of La cations in GdVO 4 NPs was quantitative (∼100%). Retention of radionuclides was assessed in vitro by dialyzing the radioactive GdVO 4 NPs against deionized water. While 227 Th was quantitatively encapsulated (100%), a partial encapsulation of 223 Ra (∼75%) and 225 Ac (>60%) was observed in GdVO 4 NPs. The maximum leakage of 221 Fr (1st decay daughter of 225 Ac) was 55.4 ± 3.6%, whereas for 223 Ra (1st decay daughter of 227 Th) the maximum leakage was 73.0 ± 4.0%. These results show the potential of GdVO 4 NPs as platforms of α -emitting radionuclides for their application in targeted alpha therapy.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Out-of-Plane Sulfur Distortions in the Bi4O4S3 Superconductor

The local atomic structure of the non-magnetic layered superconductor Bi4O4S3 was investigated using neutron diffraction and pair density function (PDF) analysis. Although on average, the crystal structure is well ordered, evidence for local, out–of–plane sulfur distortions is provided, which may act as a conduit for charge transfer from the SO4 blocks into the superconducting BiS2 planes. In contrast with LaO1−xFxBiS2, no sulfur distortions were detected in the planes, which indicates that charge density wave fluctuations are not supported in Bi4O4S3.

Philip, Sharon S. (ORCID:000000031055718X)↗

Crystal growth and magnetic structure of ternary silicide Eu Pd 3 Si 2

The hexagonal CaCu 5 –type structure (P6/mmm) is the prototype for more than 100 ternary borides, gallides, and silicides, with general stoichiometry of RTM 3 X 2 (R=lanthanide/alkaline earth; TM=transition metal; X=B, Ga, Si, Ge). Here we report the synthesis, crystal structure, and bulk magnetic properties of polycrystalline and single crystal samples of EuPd 3 Si 2 and its nonmagnetic analog SrPd 3 Si 2 . Both compounds crystallize in the orthorhombic space group symmetry Imma (no. 74, Z = 2, oI12) displaying pseudohexagonal symmetry. Ferromagnetic (FM) order of Eu 2+ at T C1 =78K and a spin-reorientation transition at T C2 =5K appear as distinctive features in bulk magnetization, specific heat, and resistivity/resistance measurements. Neutron powder diffraction measurements on EuPd 3 Si 2 confirm FM order of the Eu 2+ spins below T C1 , with the spins aligned along the a axis below T C2 . Electronic band structure calculations corroborate the crystal structure and the FM state for EuPd 3 Si 2 , with a Pd d–band polarization in the same direction as the Eu 4f polarization, enhancing the observed spin moment.

36 MATERIALS SCIENCE↗

Structural Distortions and Short‐Range Magnetism in a Honeycomb Iridate Cu 3 ZnIr 2 O 6

Layered honeycomb iridates receive significant attention in the materials chemistry and physics fields due to the relevance of their crystal structures to the Kitaev model of a quantum spin liquid (QSL). In quest of liquid‐like magnetic ground state signatures, first‐generation alkali metal iridates A 2 IrO 3 ≡ A 3 [AIr 2 ]O 6 (A = Li, Na) and second‐generation iridates T 3 [AIr 2 ]O 6 ( T = Cu, Ag, H) are developed. T 3 [AIr 2 ]O 6 is synthesized from A 3 [AIr 2 ]O 6 via metathesis reactions replacing alkali ions located between honeycomb layers. Herein, the next level of chemical and structural complexity is introduced by synthesizing the honeycomb iridate, Cu 3 ZnIr 2 O 6 , in which alkali ions between and within the honeycomb layers are both selectively exchanged with two different transition metals. Analysis of powder X‐Ray diffraction data reveals corrugation of the honeycomb layers in Cu 3 ZnIr 2 O 6 that hinders complete magnetic frustration and results in a spin glass behavior observed from magnetization and specific heat data. Thus, Cu 3 ZnIr 2 O 6 represents yet another model, which broadens understanding of intricate relationships between intralayer distortions and magnetism of prospective Kitaev QSL compounds.

36 MATERIALS SCIENCE↗

Magnetization distribution in Cu 0.6 Mn 2.4 Ge 2 ferromagnet from polarized and non-polarized neutron powder diffraction aided by density-functional theory calculations

The crystal structure and magnetic properties of Cu 0.6 Mn 2.4 Ge 2 have been re-investigated by a combination of extensive magnetic measurements and neutron scattering experiments, aided by electronic structure calculations. The material is found to be a soft ferromagnet with the ordering temperature T C = 316 K. The magnetocaloric effect evaluated from field-dependent magnetization isotherms is equal to 1.2 J/(kg·K) and 2.5 J/(kg·K) under the maximum applied magnetic field of 2 T and 5 T, respectively. The compound crystallizes in the hexagonal space group P6 3 /mmc. A complex structural disorder necessitated testing of several disorder models against the results of non-polarized and polarized neutron scattering experiments and magnetization measurements. Simulations at the density-functional theory level were also performed to identify the most robust solution that properly described the data observed. The final magnetic structure model reveals non-equal magnetic moments on the Mn1 and Mn2 atoms (2.29(9) µ B and 2.7(1) µ B , respectively) and the presence of vacancies and minor Cu substitution defects in both Mn sites. The work demonstrates how the non-polarized and polarized neutron scattering methods can be combined with electronic structure calculations to establish the microscopic structure of magnetic materials with complex crystallographic disorder.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Scattering Studies of Superconducting Vacancy‐Ordered Monoclinic TiO Thin Films

Abstract The structural and transport properties of vacancy‐ordered monoclinic superconducting titanium oxide (TiO) thin films grown by molecular beam epitaxy are investigated. The evolution of the crystal structure during growth is monitored by in situ synchrotron X‐ray diffraction. Long‐range ordering of Ti and O vacancies in the disordered cubic phase stabilizes the vacancy‐ordered monoclinic TiO phase. The reduced structural disorder arising from vacancy‐ordering is correlated with a superconductor‐metal transition (SMT) in contrast to the superconductor‐insulator transition (SIT) observed in cubic TiO, orthorhombic Ti 2 O 3 , and the Magneli γ − Ti 3 O 5 and γ − Ti 4 O 7 phase. Magnetoresistance measurements for the SIT phases indicate superconducting fluctuations persisting in the normal phase. These results confirm the role of disorder related to Ti and O vacancies and structural inhomogeneity in determining the electronic properties of the normal state of titanium oxide‐based superconductors.

Baksi, Merve↗

Linear Dichroism of the Optical Properties of SnS and SnSe Van der Waals Crystals

Abstract Tin monochalcogenides SnS and SnSe, belonging to a family of Van der Waals crystals isoelectronic to black phosphorus, are known as environmentally friendly materials promising for thermoelectric conversion applications. However, they exhibit other desired functionalities, such as intrinsic linear dichroism of the optical and electronic properties originating from strongly anisotropic orthorhombic crystal structures. This property makes them perfect candidates for polarization‐sensitive photodetectors working in near‐infrared spectral range. A comprehensive study of the SnS and SnSe crystals is presented, performed by means of optical spectroscopy and photoemission spectroscopy, supported by ab initio calculations. The studies reveal the high sensitivity of the optical response of both materials to the incident light polarization, which is interpreted in terms of the electronic band dispersion and orbital composition of the electronic bands, dictating the selection rules. From the photoemission investigation the ionization potential, electron affinity and work function are determined, which are parameters crucial for the design of devices based on semiconductor heterostructures.

Chemistry↗

Structural, magnetic, and magnetocaloric properties of (Nd 0.7 Ce 0.3 )YFe 17

Structural, magnetic, and magnetocaloric properties of iron-deficient (Nd 1-x Ce x )YFe 17 alloys in the rhombohedral Th 2 Zn 17 –type crystal structure prepared by arc-melting and vacuum annealing have been investigated. Among the investigated alloys, (Nd 0.7 Ce 0.3 )YFe 17 shows the highest values of magnetic entropy change and relative cooling power, namely 5.45 J kg -1 K -1 and 504 J kg -1 for a magnetic field change of 5 T. The Curie temperature and saturation magnetization of the (Nd 0.7 Ce 0.3 )YFe 17 alloy are 301 K and 162 emu/g, respectively. The absence of thermal and magnetic hysteresis with relatively high cooling capacity near room temperature suggests that Fe-deficient (Nd 0.7 Ce 0.3 )YFe 17 carries significant potential for room-temperature magnetic refrigeration.

36 MATERIALS SCIENCE↗

Development of Porous Crystalline Materials for Selective Binding of O 2 from Air

Porous materials that take advantage of different chemisorptive behaviors of O 2 and N 2 could be an effective alternative to approaches based on physisorption for this important separation. Recently, the tetra-nuclear cobalt complex [(Co(III) 2 (bpbp)O 2 ) 2 bdc](PF 6 ) 4 (CSD code: GAMVIB; bpbp – = 2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-tert-butylphenolato; bdc 2– = 1,4-benzenedicarboxylato) was shown to have potential for O 2 /N 2 separations based on this concept. This observation raises the question of what other known materials have similar properties. Here, we combine structure screening with a high-throughput periodic density functional theory (DFT) workflow to investigate O 2 and N 2 adsorption in materials from validated crystal structure databases (e.g., CoRE-MOF database and CSD database). These calculations identify multiple materials that have similar di-Co clusters to GAMVIB that are predicted to selectively bind O 2 over N 2 , and suggest design rules that can be used to tune the O 2 and N 2 affinities in materials of this kind.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

De novo design of buttressed loops for sculpting protein functions

In natural proteins, structured loops have central roles in molecular recognition, signal transduction and enzyme catalysis. However, because of the intrinsic flexibility and irregularity of loop regions, organizing multiple structured loops at protein functional sites has been very difficult to achieve by de novo protein design. Here we describe a solution to this problem that designs tandem repeat proteins with structured loops (9–14 residues) buttressed by extensive hydrogen bonding interactions. Experimental characterization shows that the designs are monodisperse, highly soluble, folded and thermally stable. Crystal structures are in close agreement with the design models, with the loops structured and buttressed as designed. We demonstrate the functionality afforded by loop buttressing by designing and characterizing binders for extended peptides in which the loops form one side of an extended binding pocket. The ability to design multiple structured loops should contribute generally to efforts to design new protein functions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

RNA polymerase II trapped on a molecular treadmill: Structural basis of persistent transcriptional arrest by a minor groove DNA binder

Elongating RNA polymerase II (Pol II) can be paused or arrested by a variety of obstacles. These obstacles include DNA lesions, DNA-binding proteins, and small molecules. Hairpin pyrrole-imidazole (Py-Im) polyamides bind to the minor groove of DNA in a sequence-specific manner and induce strong transcriptional arrest. Remarkably, this Py-Im–induced Pol II transcriptional arrest is persistent and cannot be rescued by transcription factor TFIIS. In contrast, TFIIS can effectively rescue the transcriptional arrest induced by a nucleosome barrier. The structural basis of Py-Im–induced transcriptional arrest and why TFIIS cannot rescue this arrest remain elusive. Here we determined the X-ray crystal structures of four distinct Pol II elongation complexes (Pol II ECs) in complex with hairpin Py-Im polyamides as well as of the hairpin Py-Im polyamides–dsDNA complex. We observed that the Py-Im oligomer directly interacts with RNA Pol II residues, introduces compression of the downstream DNA duplex, prevents Pol II forward translocation, and induces Pol II backtracking. These results, together with biochemical studies, provide structural insight into the molecular mechanism by which Py-Im blocks transcription. Our structural study reveals why TFIIS fails to promote Pol II bypass of Py-Im–induced transcriptional arrest.

59 BASIC BIOLOGICAL SCIENCES↗

Structural dissection of sequence recognition and catalytic mechanism of human LINE-1 endonuclease

Abstract Long interspersed nuclear element-1 (L1) is an autonomous non-LTR retrotransposon comprising ∼20% of the human genome. L1 self-propagation causes genomic instability and is strongly associated with aging, cancer and other diseases. The endonuclease domain of L1’s ORFp2 protein (L1-EN) initiates de novo L1 integration by nicking the consensus sequence 5′-TTTTT/AA-3′. In contrast, related nucleases including structurally conserved apurinic/apyrimidinic endonuclease 1 (APE1) are non-sequence specific. To investigate mechanisms underlying sequence recognition and catalysis by L1-EN, we solved crystal structures of L1-EN complexed with DNA substrates. This showed that conformational properties of the preferred sequence drive L1-EN’s sequence-specificity and catalysis. Unlike APE1, L1-EN does not bend the DNA helix, but rather causes ‘compression’ near the cleavage site. This provides multiple advantages for L1-EN’s role in retrotransposition including facilitating use of the nicked poly-T DNA strand as a primer for reverse transcription. We also observed two alternative conformations of the scissile bond phosphate, which allowed us to model distinct conformations for a nucleophilic attack and a transition state that are likely applicable to the entire family of nucleases. This work adds to our mechanistic understanding of L1-EN and related nucleases and should facilitate development of L1-EN inhibitors as potential anticancer and antiaging therapeutics.

59 BASIC BIOLOGICAL SCIENCES↗

Nonexcitonic mechanism for electronic and structural phase transitions in Ta 2 ⁢Ni⁢(Se,S) 5

Here, we present a first-principles study based on density functional theory (DFT) on the electronic and structural properties of Ta 2 NiSe 5 , a layered transition metal chalcogenide that has been considered as a possible candidate for an excitonic insulator. Our systematic DFT results however provide a nonexcitonic mechanism for the experimentally observed electronic and structural phase transitions in Ta 2 NiSe 5 , in particular explaining why sulfur substitution of selenium reduces the distortion angle in the low-temperature phase and potassium dosing closes the gap in the electronic structure. Moreover, the calculations show that these two effects couple to each other. Further, our first-principles calculations predict several changes in both the crystal structure and electronic structure under the effects of uniform charge dosing and uniaxial strain, which could be tested experimentally.

Tang, Weichen [University of California, Berkeley,↗

Structure refinement and anisotropic atomic displacement parameters of 1M Illite: Rietveld and pair distribution function analysis using synchrotron X-ray radiation

Illite, a widespread clay mineral, plays a pivotal role in geological processes, notably as an indicator in diagenetic and hydrothermal alteration environments, and possesses significant industrial relevance in applications including ceramics, construction and catalysis. However, challenges including its nanoscale crystallinity, structural disorder and frequent interstratification with other clay minerals have hindered detailed structural characterization using conventional X-ray diffraction (XRD) techniques. This study employs integrated synchrotron XRD and pair distribution function (PDF) analysis to elucidate the crystal structure of the 1M illite polytype, yielding the first determination of its anisotropic atomic displacement parameters (U aniso ). TheseU aniso parameters provide critical insights into atomic dynamics and static disorder within the structure, enabling a more refined understanding of structure–property relationships. This integrated approach, combining synchrotron XRD, Rietveld refinement and PDF analysis, yields a comprehensive structural characterization, capturing both average crystallographic and local atomic arrangements. Considering illite's widespread geological occurrence and industrial importance, this high-precision structural dataset, especially the determinedU aniso values, provides a crucial benchmark for future modeling and simulation efforts targeting accurate prediction of its physicochemical behavior.

Chemistry↗