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2022 • Chemical Communications

Photoacoustic measurement of localized optical dichroism in chiral crystals

Gil Otis, Matan Benyamin, Yitzhak Mastai, Zeev Zalevsky

In this communication, we present a novel method to measure local optical dichroism (OD) in opaque crystal powder suspensions using photoacoustic (PA) effect. Our method is based upon the novel laser speckle contrast technique, in combination with a simple statistical approach, we were able to measure the OD of chiral crystals suspensions under completely random orientation.

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2022 • CHEMICAL BULLETIN

GA Seilkhanova1, 2*, AB Rakhym1, 2, AV Kan1, AK Kenessova1, 2

Yitzhak Mastai

In this work, sorbents based on natural zeolite (Z) and chamotte clay (ChC) treated with NaCl and HNO3 solutions were obtained to extract Na+ and K+ ions from saline water. The physicochemical characteristics of the obtained sorbents were studied by SEM, EDAX, and BET methods. It was found that successive treatment with NaCl and HNO3 solutions has a positive effect on the sorption properties of the studied materials. The maximum increase in the specific surface area from 4.5 m2/g to 39.3 m2/g is observed for acid-treated Z, and the specific surface area of ChC also increases almost 2-fold from 8.4 m2/g to 15.3 m2/g. Na+ and K+ ions are extracted from water due to ion exchange with Z and ChC cations. As a result of determining the cation exchange capacity (CEC) of the studied sorbents, it was found that treatment with a NaCl solution improves the ion exchange properties of the sorbent and leads to the formation of a “homoionic” form of aluminosilicates. Due to that the sorbents more easily enter ion exchange reactions. The authors established the sorption activity of the obtained materials based on natural Z and ChC with respect to Na+ and K+ cations. The maximum recovery rate is 28.45% for Na+ ions with the ChC-Na-H sorbent and 76.28% for K+ ions with the ChC-Na sorbent. Among Z-based sorbents, the most effective forms are Z-Na-H (15.44% Na+ recovery) and Z-Na (60.47% K+ recovery).

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2022 • Polymers 14 (14), 2765-2765, 2022

Chiral Porous Carbon Surfaces for Enantiospecific Synthesis.

SS Aloni, M Nassir, Y Mastai

Chiral surfaces, developed in the last decade, serve as media for enantioselective chemical reactions. Until today, they have been based mostly on developments in silica templating, and are made mainly from imprints of silicate materials developed a long time ago. Here, a chiral porous activated carbon surface was developed based on a chiral ionic liquid, and the surface chemistry and pore structure were studied to lay a new course of action in the field. The enantioselectivities of surfaces are examined by using variety of methods such as circular dichroism, linear sweep voltammetry and catalysis. These techniques revealed a 28.1% preference for the D enantiomer of the amino acid proline, and linear sweep voltammetry confirmed chirality recognition by another probe. An aldol surface chiral catalytic reaction was devised and allowed to determine the root of the enantiomeric excess. These results affirm the path …

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2022 • Advanced Materials Interfaces

Growth of Hybrid Chiral Thin Films by Molecular Layer Deposition Zinc/Cysteine as a Case Study

Reut Yemini, Shalev Blanga, Hagit Aviv, Ilana Perelshtein, Eti Teblum, Shahar Dery, Elad Gross, Yitzhak Mastai, Malachi Noked, Ortal Lidor‐Shalev

Atomic and molecular layer deposition (ALD and MLD) are techniques based on surface‐directed self‐limiting reactions that afford deposition of films controlled at the monolayer level and with extreme conformality, even on ultra‐high‐aspect‐ratio and porous substrates. These methodologies are typically used to deposit thin films with desirable physical properties and functionality. Here, the MLD process is harnessed to demonstrate the growth of molecularly thin chiral films that inherit a desirable chemical property directly from the source precursor: using this innovative technique, enantioselective nanosurfaces are managed to be grown. Specifically, the formation of a Zn/Cysteine nanostructure by MLD is demonstrated for both the l‐ and d‐ enantiomers. The reaction and growth mechanism of these chiral hybrid inorganic‐organic nanosurfaces are studied via various experimental procedures; their …

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2022 • Polymers for Advanced Technologies

Electrospinning of polymer nanofibers based on chiral polymeric nanoparticles

Meir Abuaf, Yitzhak Mastai


2022 • s Note: MDPI stays neutral with regard to jurisdictional claims in published …, 2022

Acoustic Manipulation of Intraocular Particles. Micromachines 2022, 13, 1362

A Leshno, A Kenigsberg, H Peleg-Levy, S Piperno, A Skaat, H Shpaisman

Various conditions cause dispersions of particulate matter to circulate inside the anterior chamber of a human eye. These dispersed particles might reduce visual acuity or promote elevation of intraocular pressure (IOP), causing secondary complications such as particle related glaucoma, which is a major cause of blindness. Medical and surgical treatment options are available to manage these complications, yet preventive measures are not currently available. Conceptually, manipulating these dispersed particles in a way that reduces their negative impact could prevent these complications. However, as the eye is a closed system, manipulating dispersed particles in it is challenging. Standing acoustic waves have been previously shown to be a versatile tool for manipulation of bioparticles from nano-sized extracellular vesicles up to millimeter-sized organisms. Here we introduce for the first time a novel method utilizing standing acoustic waves to noninvasively manipulate intraocular particles inside the anterior chamber. Using a cylindrical acoustic resonator, we show ex vivo manipulation of pigmentary particles inside porcine eyes. We study the effect of wave intensity over time and rule out temperature changes that could damage tissues. Optical coherence tomography and histologic evaluations show no signs of damage or any other side effect that could be attributed to acoustic manipulation. Finally, we lay out a clear pathway to how this technique can be used as a non-invasive tool for preventing secondary glaucoma. This concept has the potential to control and arrange intraocular particles in specific locations without causing any damage to …

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2022 • Frontiers in Molecular Biosciences

Disrupting Cu trafficking as a potential therapy for cancer

Zena Qasem, Matic Pavlin, Ida Ritacco, Matan Y Avivi, Shelly Meron, Melanie Hirsch, Yulia Shenberger, Lada Gevorkyan-Airapetov, Alessandra Magistrato, Sharon Ruthstein

Copper is an essential trace element required for vital cell functions and the survival of all organisms, ranging from bacteria to humans (Burkhead et al., 2009; Gaggelli et al., 2009; Lutsenko, 2010). Owing to the ability of copper to cycle between two oxidation states [ie, Cu (I) and Cu (II)], copper ions serve as important catalytic cofactors in proteinlinked redox chemistry. Such proteins carry out fundamental biological functions and are required for proper cellular growth and development. Copper-dependent proteins are involved in a wide variety of biological processes. Therefore, copper deficiency in these enzymes and/or alterations in their functions often trigger disease states or physiopathological conditions. Although critical for proper cell functioning, copper ions can also act as potent cytotoxins (Bertinato and L’Abbe, 2004; Manto, 2014; Harrison and Dameron, 1999). Owing to its special redox chemistry, copper …

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2022 • s Note: MDPI stays neutral with regard to jurisdictional claims in published …, 2022

Nitrogen Structure Determination in Treated Fancy Diamonds via EPR Spectroscopy. Crystals 2022, 12, 1775

I Litvak, A Cahana, Y Anker, S Ruthstein, H Cohen

Color induction in nitrogen-contaminated diamonds was carried out via various procedures that involve irradiation, thermal treatments (annealing), and more. These treatments affect vacancy defect production and atom orientation centers in the diamond lattice. Natural diamonds underwent color enhancement treatments in order to produce green, blue, and yellow fancy diamonds. The aim of this study was to follow the changes occurring during the treatment, mainly by EPR spectroscopy, which is the main source for the determination of the effect of paramagnetic centers (carbon-centered radicals) on the color centers produced via the treatments, but also via visual assessment, fluorescence, UV-vis, and FTIR spectroscopy. The results indicate that diamonds containing high levels of nitrogen contamination are associated with high carbon-centered radical concentrations. Four paramagnetic center structures (N1, N4, and P2/W21) were generated by the treatment. It is suggested that the N4 structure correlates with the formation of blue color centers, whereas yellow color centers are attributed to the presence of N1 species. While to produce blue and yellow colors, a thermal treatment is needed after irradiation, for treated green diamonds, no thermal treatment is needed (only irradiation).

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2022 • Physical Chemistry Chemical Physics

The effects of thermal treatment and irradiation on the chemical properties of natural diamonds

Ira Litvak, Haim Cohen, Sharon Ruthstein, Yaakov Anker, Avner Cahana

The modification of nitrogen-contaminated diamonds into color-enhanced diamonds is usually achieved by irradiation and thermal treatment (annealing). These treatments affect nitrogen contamination chemical bonding, vacancy concentration, and atom orientation centers in the diamond lattice. In this study, natural diamonds were subjected to irradiation and thermal annealing color enhancement treatments to produce green, blue, and yellow fancy diamonds. The study followed the changes that occur during treatment relying on visual assessment, fluorescence, UV-vis, FTIR, and EPR spectroscopy to characterize paramagnetic centers. The results indicated that diamonds containing high levels of nitrogen contamination presented a relatively high carbon-centered radical concentration. Two paramagnetic groups with different g-values were found, namely, low g-value centers of 2.0017-2.0027 and high g-value …

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2022 • Chemical Science

Cu (II)-based DNA Labeling Identifies the Structural Link Between Activation and Termination in a Metalloregulator

Joshua Casto, Alysia Mandato, Lukas Hofmann, Idan Yakobov, Shreya Ghosh, Sharon Ruthstein, Sunil Saxena

Understanding the structural and mechanistic details of protein-DNA interactions that lead to cellular defence against toxic metal ions in pathogenic bacteria can lead to new ways of combating their virulence. Herein, we examine the Copper Efflux Regulator (CueR) protein, a transcription factor which interacts with DNA to generate proteins that ameliorate excess free Cu(I). We exploit site directed Cu(II) labeling to measure the conformational changes in DNA as a function of protein and Cu(I) concentration. Unexpectedly, the EPR data indicates that the protein can bend the DNA at high protein concentrations even in the Cu(I)-free state. On the other hand, the bent state of the DNA is accessed at a low protein concentration in the presence of Cu(I). Such bending enables the coordination of the DNA with RNA polymerase. Taken together, the results lead to a structural understanding of how transcription is activated in …

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2022

Antibacterial properties and mechanisms of action of sonoenzymatically synthesized lignin-based nanoparticles

Morena Gatius, Ángela Gala, Arnau Bassegoda Puigdomenech, Michal Natan, Gila Jacobi, Ehud Banin, Tzanko Tzanov

In recent years, lignin has drawn increasing attention for different applications due to its intrinsic antibacterial and antioxidant properties, coupled with biodegradability and biocompatibility. However, chemical modification or combination with metals is usually required to increase its antimicrobial functionality and produce biobased added-value materials for applications wherein bacterial growth should be avoided, such as biomedical and food industries. In this work, a sonoenzymatic approach for the simultaneous functionalization and nanotransformation of lignin to prepare metal-free antibacterial phenolated lignin nanoparticles (PheLigNPs) is developed. The grafting of tannic acid, a natural phenolic compound, onto lignin was achieved by an environmentally friendly approach using laccase oxidation upon the application of high-intensity ultrasound to rearrange lignin into NPs. PheLigNPs presented higher …

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2022 • Advanced Functional Materials

Sulfur‐Treatment Passivates Bulk Defects in Sb2Se3 Photocathodes for Water Splitting

Rajiv Ramanujam Prabhakar, Thomas Moehl, Dennis Friedrich, Marinus Kunst, Sudhanshu Shukla, Damilola Adeleye, Vinayaka H Damle, Sebastian Siol, Wei Cui, Laxman Gouda, Jihye Suh, Yaakov R Tischler, Roel van de Krol, S David Tilley

Sb2Se3 has emerged as an important photoelectrochemical (PEC) and photovoltaic (PV) material due to its rapid rise in photoconversion efficiencies. However, Sb2Se3 has a complex defect chemistry, which reduces the maximum photovoltage. Thus, it is important to understand these defects and develop defect passivation strategies in Sb2Se3. A comprehensive investigation of the charge carrier dynamics of Sb2Se3 and the influence of sulfur treatment on its optoelectronic properties is performed using time‐resolved microwave conductivity (TRMC), photoluminescence (PL) spectroscopy, and low‐frequency Raman spectroscopy (LFR). The key finding in this work is that upon sulfur treatment of Sb2Se3, the carrier lifetime is increased by the passivation of deep defects in Sb2Se3 in both the surface region and the bulk, which is evidenced by increased charge carrier lifetime of TRMC decay dynamics, increased …

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2022 • Advanced Photonics Research

Coupled Molecular Emitters in Superstructures Interact with Plasmonic Nanoparticles

Daniel Beitner, Itai Carmeli, Zeev Zalevsky, Shachar Richter, Haim Suchowski

Using hyperspectral measurements, J‐aggregate nanorods of porphyrin molecules embedded in plasmonic Au nanoparticles arrays are studied. Measurements of J‐aggregate nanorods that cross onto a plasmonic array exhibit a shift in their absorption peak, and display weak coupling properties only for the embedded part. Furthermore, a significant thickness‐dependent redshift in the plasmonic resonance for the J‐aggregate clusters is observed. Such redshift is also dependent on the ratio of J‐aggregate in the plasmonic dipole interaction area, reaching values of up to 120 meV for ≈40% coverage. In addition, for large clusters of J‐aggregates, the plasmonic spectrum shows coupling behavior between the systems indicated by a small Rabi splitting. The findings are validated by a quasi‐static model based on the change of the dielectric environment around the embedded nanoparticles. Using the model, the …

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2022 • s Note: MDPI stays neutral with regard to jurisdictional claims in published …, 2022

Magnetite nanoparticles: Synthesis and applications in optics and nanophotonics. Materials 2022, 15, 2601

N Dudchenko, S Pawar, I Perelshtein, D Fixler

Magnetite nanoparticles with different surface coverages are of great interest for many applications due to their intrinsic magnetic properties, nanometer size, and definite surface morphology. Magnetite nanoparticles are widely used for different medical-biological applications while their usage in optics is not as widespread. In recent years, nanomagnetite suspensions, so-called magnetic ferrofluids, are applied in optics due to their magneto-optical properties. This review gives an overview of nanomagnetite synthesis and its properties. In addition, the preparation and application of magnetic nanofluids in optics, nanophotonics, and magnetic imaging are described.

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2022 • Micro-and Nano-containers for Smart Applications, 127-153, 2022

Containers for drug delivery

Sayan Ganguly, Poushali Das, Shlomo Margel

Precise delivery of therapeutic cargos to the destined location is a medical demand for desirable physiological responses. In this discussion the synthetic approaches to prepare cargos and their mode of delivery have been addressed. The versatile synthesis and materialistic approaches have revealed by various scientists that besides carrying drugs/biomolecules the protection is also needed. The merits and demerits of those various architectural units also have been discussed in brief to assess their acceptability and mode of usages.

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2022 • Physical Chemistry Chemical Physics

Cu 2+-Induced self-assembly and amyloid formation of a cyclic d, l-α-peptide: structure and function

Daniel Klose, Sahithya Phani Babu Vemulapalli, Michal Richman, Safra Rudnick, Vered Aisha, Meital Abayev, Marina Chemerovski, Meital Shviro, David Zitoun, Katharina Majer, Nino Wili, Gil Goobes, Christian Griesinger, Gunnar Jeschke, Shai Rahimipour

In a wide spectrum of neurodegenerative diseases, self-assembly of pathogenic proteins to cytotoxic intermediates is accelerated by the presence of metal ions such as Cu2+. Only low concentrations of these early transient oligomeric inter-mediates are present in a mixture of species during fibril formation, and hence information on the extent of structuring of these oligomers is still largely unknown. Here, we investigate dimers as the first intermediates in the Cu2+-driven aggrega-tion of a cyclic D,L-α-peptide architecture. The unique structural and functional properties of this model system recapitu-late the self-assembling properties of amyloidogenic proteins including β-sheet conformation and cross-interaction with pathogenic amyloids. We show that a histidine-rich cyclic D,L-α-octapeptide binds Cu2+ with high affinity and selectivity to generate amyloid-like cross-β-sheet structures. By taking advantage of …

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2022 • Energy & Environmental Science

Light-induced beneficial ion accumulation for high-performance quasi-2D perovskite solar cells

Xiaomei Lian, Lijian Zuo, Bowen Chen, Biao Li, Haotian Wu, Shiqi Shan, Gang Wu, Xuegong Yu, Qi Chen, Liwei Chen, Deren Yang, David Cahen, Hongzheng Chen

Ion migration and subsequent accumulation at interfaces, driven by the built-in potential (Vbi), are intrinsic properties of halide perovskite solar cells (PVSCs), which mostly decrease the device performance. To address this issue, we constructed favorable ion accumulation in perovskite solar cells via illumination to improve the performance of the quasi-2D PVSCs. This design dramatically improves the photo-carrier collection and enables significant device performance improvement from 14.6% to 19.05%, one of the best results for quasi-2D PVSCs. We argue that the light-triggered favorable ion accumulation originates from (1) the photo-induced quasi-Fermi level splitting that compensates the Vbi, so as to avoid the ion accumulation that decreases Vbi, and (2) the light-intensity-distribution-induced uneven ion potential further drives the segregation of mobile ions towards favorable ion accumulation, decreasing any …

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2022 • Frontiers in Immunology

A BALB/c IGHV reference set, defined by haplotype analysis of long-read VDJ-c sequences from F1 (BALB/cx C57BL/6) mice

Katherine JL Jackson, Justin T Kos, William Lees, William S Gibson, Melissa Laird Smith, Ayelet Peres, Gur Yaari, Martin Corcoran, Christian E Busse, Mats Ohlin, Corey T Watson, Andrew M Collins

The immunoglobulin genes of inbred mouse strains that are commonly used in models of antibody-mediated human diseases are poorly characterized. This compromises data analysis. To infer the immunoglobulin genes of BALB/c mice, we used long-read SMRT sequencing to amplify VDJ-C sequences from F1 (BALB/cx C57BL/6) hybrid animals. Strain variations were identified in the Ighm and Ighg2b genes, and analysis of VDJ rearrangements led to the inference of 278 germline IGHV alleles. 169 alleles are not present in the C57BL/6 genome reference sequence. To establish a set of expressed BALB/c IGHV germline gene sequences, we computationally retrieved IGHV haplotypes from the IgM dataset. Haplotyping led to the confirmation of 162 BALB/c IGHV gene sequences. A musIGHV398 pseudogene variant also appears to be present in the BALB/cByJ substrain, while a functional musIGHV398 gene is …

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2022 • Proc. of SPIE Vol

Quantum hard x-ray microscopy with undetected photons

Haim Aknin, Sharon Shwartz

We explore the possibility for implementing nanoscale quantum imaging based on the concept of undetected photons with a pumping beam at x-ray wavelengths. Our proposed scheme exploits the nearly four order of magnitude angular magnification that is a result of the process of the effect of extreme non-degenerate spontaneous down conversion from xrays into optical radiation, which is used for the generation of entangled photon pairs with one x-ray photon and one visible photon. In our scheme the x-ray photons interact with the object and the visible do not interact with the object, but in contrast to other schemes like ghost imaging, only the visible photons are detected. The scheme is sensitive to both the amplitude and the phase variations and can provide resolutions down to a few nanometers, hence can be used as a powerful tool for nanoscale imaging. In the present configuration, the scheme requires very …

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2022 • Chemical Communications

Redox-and metal-directed structural diversification in designed metalloprotein assemblies

Albert Kakkis, Eyal Golub, Tae Su Choi, F Akif Tezcan

Herein we describe a designed protein building block whose self-assembly behaviour is dually gated by the redox state of disulphide bonds and the identity of exogenous metal ions. This protein construct is shown – through extensive structural and biophysical characterization – to access five distinct oligomeric states, exemplifying how the complex interplay between hydrophobic, metal–ligand, and reversible covalent interactions could be harnessed to obtain multiple, responsive protein architectures from a single building block.

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2022 • APS March Meeting Abstracts

Designing chromium (IV) molecular color centers

Daniel Laorenza, Arailym Kairalapova, Samuel Bayliss, Tamar Goldzak, Samuel Greene, Leah Weiss, Pratiti Deb, Peter Mintun, Kelsey Collins, David Awschalom, Timothy Berkelbach, Danna Freedman

Transition metal-based molecular spins are a promising class of chemically tunable quantum bits (qubits), providing precise control over both the physical and electronic structure within a scalable qubit platform. However, molecular systems typically lack an optically addressable ground state spin. To introduce this valuable resource into molecular spins, we recently created a series of chromium (IV) compounds with the desired optical-spin interface through bottom-up design [1]. Here, we illustrate the versatility of this methodology to generate designer molecular color centers by modifying the organic moieties, or ligands, directly bound to the chromium (IV) site. Variation of the surrounding ligands across six unique systems modulates both the optical emission and ground state zero-field splitting (ZFS) energies. Moreover, the small ZFS values allowed for coherent spin manipulation at X-band microwave frequency …

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