Crystals — Open Access Journal

: The Zn(II) complex of salen-like scaffold [Zn(sal)](H₂O) was synthesized and characterized by elemental analysis, IR, UV–Vis, and ¹H-NMR spectroscopic techniques. The structure of complex was confirmed by single crystal X-ray diffraction studies. In the complex, Zn (II) was placed in the inner N₂O₂ compartment of the salen scaffold in square planar geometry and crystallized in the monoclinic space group P2₁/n. DFT and TDDFT calculations were performed to reproduce the experimentally observed structural and spectroscopic (IR and UV–vis) findings. The bonding of the Zn(II) framework in the [Zn(sal)](H₂O) complex was explored in depth. The theoretical approaches employed were perturbation theory within the context of the natural bond orbital (NBO) framework, and quantum theory of atoms in molecule (QTAIM) and electron localization function (ELF) analysis. The study begins by delineating the difference between the NBO and QTAIM approaches. This paper thus exhibits the supportive nature of NBO theory and QTAIM in discussion of the bonding in the [Zn(sal)](H₂O) complex, when both the methodologies are used in combination. Full article

For the additive manufacturing (AM) of metal objects, the powder-based fusion (PBF) method is routinely utilized to fabricate macroscale parts. On the other hand, electrochemical additive manufacturing (ECAM), in which metallic structures are deposited through the electrochemical reduction of metal ions, is a promising technique for producing micro- and nanoscale objects. However, a gap exists in terms of fabricating mesoscale objects within the current AM techniques. The PBF method is limited by fabrication precision due to pronounced residual stresses, and most current ECAM systems are difficult to scale up to print mesoscale objects. In the present paper, the novel design of a low-cost ECAM 3D printer based on a microfluidic system is proposed for fabricating mesoscale metal parts. The meniscus-guided electrodeposition approach is utilized, in which a meniscus is formed between the print head and substrate, and electrodeposition is confined within the meniscus. A 3D object is fabricated by the meniscus moving with the print head according to the programmed pattern and the material subsequently being deposited at the designated locations. The key to the proposed design is to maintain a mesoscale meniscus, which normally cannot be sustained by the electrolyte surface tension with a print nozzle having a mesoscale diameter. Therefore, a microfluidic system, called the fountain pen feed system, constituting a semi-open main channel and comb structure, was designed to maintain a mesoscale meniscus throughout the printing process. Two materials, copper and nickel, with various geometric shapes were attempted to print by the proposed ECAM system, and, during the printing process, both fluid leaking and meniscus breaking were completely prevented. Free standing tilted copper pillars with controlled angles were printed to show the ability of the proposed design in fabricating 3D structures. A copper circuit was also printed on a non-conductive substrate to demonstrate a possible application of the proposed ECAM system in the fabrication of functional electronics. Full article

Light-oxygen-voltage (LOV) domains are ubiquitous photosensory modules found in proteins from bacteria, archaea and eukaryotes. Engineered versions of LOV domains have found widespread use in fluorescence microscopy and optogenetics, with improved versions being continuously developed. Many of the engineering efforts focused on the thermal stabilization of LOV domains. Recently, we described a naturally thermostable LOV domain from Chloroflexus aggregans. Here we show that the discovered protein can be further stabilized using proline substitution. We tested the effects of three mutations, and found that the melting temperature of the A95P mutant is raised by approximately 2 °C, whereas mutations A56P and A58P are neutral. To further evaluate the effects of mutations, we crystallized the variants A56P and A95P, while the variant A58P did not crystallize. The obtained crystal structures do not reveal any alterations in the proteins other than the introduced mutations. Molecular dynamics simulations showed that mutation A58P alters the structure of the respective loop (Aβ-Bβ), but does not change the general structure of the protein. We conclude that proline substitution is a viable strategy for the stabilization of the Chloroflexus aggregans LOV domain. Since the sequences and structures of the LOV domains are overall well-conserved, the effects of the reported mutations may be transferable to other proteins belonging to this family. Full article

We describe the synthesis and characterization of [Cu(POP)(1)][PF₆], [Cu(POP)(2)][PF₆], [Cu(xantphos)(1)][PF₆], and [Cu(xantphos)(2)][PF₆] in which ligands 1 and 2 are 2-(pyridin-2-yl)quinoline and 2-(6-methylpyridin-2-yl)quinoline, respectively. With 2,2'-bipyridine (bpy) as a benchmark, we assess the impact of the extended π-system on structural and solid-state photophysical properties. The single crystal structures of [Cu(POP)(2)][PF₆], [Cu(xantphos)(1)][PF₆], and [Cu(xantphos)(2)][PF₆] were determined and confirmed a distorted tetrahedral copper(I) coordination environment in each [Cu(P^P)(N^N)]⁺ cation. The xanthene unit in [Cu(xantphos)(1)][PF₆] and [Cu(xantphos)(2)][PF₆] hosts the quinoline unit of 1, and the 6-methylpyridine group of 2. ¹H NMR spectroscopic data indicate that these different ligand orientations are also observed in acetone solution. In their crystal structures, the [Cu(POP)(2)]⁺, [Cu(xantphos)(1)]⁺, and [Cu(xantphos)(2)]⁺ cations exhibit different edge-to-face and face-to-face π-interactions, but in all cases, the copper(I) centre is effectively protected by a ligand sheath. In [Cu(POP)(2)][PF₆], pairs of cations engage in an efficient face-to-face p-stacking embrace, and we suggest that this may contribute to this compound having the highest photoluminescence quantum yield (PLQY = 21%) of the series. With reference to data from the Cambridge Structural Database, we compare packing effects and PLQY data for the complexes incorporating 2-(pyridin-2-yl)quinoline and 2-(6-methylpyridin-2-yl)quinoline, with those of the benchmark bpy-containing compounds. We also assess the effect that Cu⋯O distances in the {Cu(POP)} and {Cu(xantphos)} domains of [Cu(P^P)(N^N)][X] compounds have on solid-state PLQY values. Full article

The paper presents the results of changes in the structural characteristics, and the degree of texturing of FeNi nanostructures close in composition to permalloy compounds as a result of directed modification by gamma radiation with an energy of 1.35 MeV and doses from 100 to 500 kGy. The choices of energy and radiation doses were due to the need to modify the structural properties, which consisted of annealing the point defects that occurred during the synthesis along the entire length of the nanotubes. The initial FeNi nanostructures were polycrystalline nanotubes of anisotropic crystallite orientation, obtained by electrochemical deposition. The study found that exposure to gamma rays led to fewer defects in the structure, and reorientation of crystallites, and at doses above 300 kGy, the presence of one selected texture direction (111) in the structure. During tests of the corrosion resistance of synthesized and modified nanostructures in a PBS solution at various temperatures, it was found that exposure to gamma rays led to a significant decrease in the rate of degradation of nanotubes and an increase in the potential life of up to 20 days. It was established that at the first stage of testing, the degradation of nanostructures is accompanied by the formation of oxide inclusions, which subsequently lead to the formation of pitting corrosion and subsequent partial or complete destruction of the nanostructures. It is shown that gamma radiation is promising not only for targeted modification of nanostructures and increasing resistance to degradation, but also for increasing the rate of catalytic reactions of the PNA-PPD type. Full article

We present fully atomistic molecular dynamics (MD) simulations at 450 K of two ionic liquid crystals in the smectic phase: 1-dodecyl-3-methylimidazolium tetrafluoroborate ([C₁₂C₁im][BF₄]) and 1-dodecyl-3-methylimidazolium chloride ([C₁₂C₁im]Cl). The two systems experimentally exhibit different ranges of thermal stability of the ionic smectic phase: The chloride salt has a more stable LC phase, between 270.3 K and 377.6 K, with a range of SmA of more than 107 K. In contrast, the tetrafluoroborate salt has a smectic phase between 299.6 K and 311.6 K, with a range of mesophase of just 12 K. The MD simulations show that the chloride system is stable in the smectic phase for the 5 ns of simulation, while the tetrafluoroborate salt melts into an isotropic ionic liquid, in qualitative agreement with the experiments. Comparison of the electrostatic and van der Waals energetic contributions enables one to rationalize the observed behavior as being due to the large size of the [BF₄] anion: a larger size of the anion means a lower charge density, and therefore a weaker electrostatic interaction in the ionic layer. Full article

Undoped ZnO and group III (B, Al, Ga, and In)-doped ZnO thin films at 3% doping concentration level are dip-coated on glass substrates using a sol-gel technique. The optical properties of the as-prepared thin films are investigated using UV–Vis spectrophotometer measurements. Transmittance of all investigated thin films is found to attain high values of ≥80% in the visible region. We found that the index of refraction of undoped ZnO films exhibits values ranging between 1.6 and 2.2 and approximately match that of bulk ZnO. Furthermore, we measure and interpret nonlinear optical parameters and the electrical and optical conductivities of the investigated thin films to obtain a deeper insight from fundamental and practical points of view. In addition, the structural properties of all studied thin film samples are investigated using the XRD technique. In particular, undoped ZnO thin film is found to exhibit a hexagonal structure. Due to the large difference in size of boron and indium compared with that of zinc, doping ZnO thin films with these two elements is expected to cause a phase transition. However, Al-doped ZnO and Ga-doped ZnO thin films preserve the hexagonal phase. Moreover, as boron and indium are introduced in ZnO thin films, the grain size increases. On the other hand, grain size is found to decrease upon doping ZnO with aluminum and gallium. The drastic enhancement of optical properties of annealed dip-synthesized undoped ZnO thin films upon doping with group III metals paves the way to tune these properties in a skillful manner, in order to be used as key candidate materials in the fabrication of modern optoelectronic devices. Full article

Serial Femtosecond Crystallography (SFX) at X-ray Free electron Lasers (XFELs) is a relatively new field promising to deliver unparalleled spatial and temporal resolution on biological systems and there dynamics. Over the past decade, though, there have been a handful of results that have truly delivered on these promises. Why? SFX has many paradigm shifting techniques not seen in typical structural biology arenas, such as creating a concentrated slurry of microcrystals rather than a handful of loopable prisms worthy of a catalog photo. Then taking that slurry and high speed jetting them towards the vacuum or helium interation region to destroy less than 1% of your sample and waste the other 99. The literature is full of techniques and methods promising to cure what ails your experiment, yet as an instrument scientist will tell you –and a first author might admit after a few drinks at the conference happy hour—is that there are a lot more failures than the success we published, results may vary. We will walk through a best practices on how to prepare your sample and chose a sample delivery technique that will amerliorate your studies rather than undermine your hardwork and hopefully lead to better experimental planning and execution, inching you closer to that scientific goal and that call from Stockholm. This will be written in a more editorialized fashion and is meant to give the reader an idea of what to try or how they should be thinking. Welcome to SFX, now what? Full article

Europium-doped hydroxyapatite Ca₁₀(PO₄)₆(OH)₂ (3% mol) powders were synthesized by an optimized chemical precipitation method at 25 °C, followed by drying at 120 °C and calcination at 450 °C and 900 °C. The obtained nanosized crystallite samples were investigated by means of a combination of inductively coupled plasma (ICP) spectroscopy, powder X-ray diffraction (PXRD), Fourier Transform Infrared (FTIR), Raman and photoluminescence (PL) spectroscopies. The Rietveld refinement in the hexagonal P6₃/m space group showed europium ordered at the Ca2 site at high temperature (900 °C), and at the Ca1 site for lower temperatures (120 °C and 450 °C). FTIR and Raman spectra showed slight band shifts and minor modifications of the (PO₄) bands with increasing annealing temperature. PL spectra and decay curves revealed significant luminescence emission for the phase obtained at 900 °C and highlighted the migration of Eu from the Ca1 to Ca2 site as a result of increasing calcinating temperature. Full article

In the present work, a layer of 75%Cr₃C₂−25%NiCr with thickness of 260 ± 15 µm was coated onto the API-2H pipeline steel surface using high-velocity oxy-fuel deposition. The effect of 75%Cr₃C₂−25%NiCr coating on the corrosion of the API steel after 1 h, 24 h, and 48 h exposure in 4.0% sodium chloride solutions is reported. The corrosion tests were performed using potentiodynamic cyclic polarization, electrochemical impedance spectroscopy, and chronoamperometric current–time techniques along with scanning electron microscopy and energy-dispersive X-ray analyses. The curves of polarization indicated that the presence of the coating increases the corrosion resistance of the steel through decreasing its corrosion current and corrosion rate. Impedance data showed that all resistances recorded higher values for the coated API steel. Chronoamperometric current–time measurements confirmed that the coated API steel has lower absolute current values and thus lower corrosion rate. All results proved that the presence of 75%Cr₃C₂−25%NiCr coating enhances the corrosion resistance of the API steel via the formation of a protective layer of Cr and Ni oxides, which could lead to decreasing the corrosion rate. Full article

To meet the demand for efficient and reliable copper and aluminum (Cu/Al) joints in refrigeration and electric power industries, interfacial reactions in 3003 Al/T2 Cu and 1035 Al/T2 Cu joints brazed by Zn-xAl (x ranged from 2–25 wt.%) filler metals and their effects on the mechanical properties of the joints were investigated. Microstructures and fracture surfaces were observed combining with composition analysis. For 3003 Al/Cu joints, bulk CuAl and CuAl₂ intermetallic compound (IMC) formed in brazing seams, and a CuAl IMC layer formed at the Cu side interfaces. For 1035 Al/Cu joints, bulk CuAl₂ IMC formed in brazing seams, and an Al_4.2Cu_3.2Zn_0.7 IMC layer formed at the Cu side interfaces. For both kinds of joints, shear strength increased first, then decreased with the increasing Al content. The increase in shear strength was because Al promoted the formation of Cu-Al IMC, and caused dispersion strengthening. With the excessive Al content, however, the bulk IMC became coarse and the IMC layers at Cu side interfaces grew thick, causing the joint strength to decrease due to stress concentration. The strength of 3003 Al/Cu joints was always higher than that of 1035 Al/Cu, and their highest strength were achieved by Zn-12Al and Zn-15Al, respectively. Full article

The effects of three main factors, including polypropylene fiber content, composite cement content and curing time on the unconfined compressive strength of fiber-reinforced cemented clay were studied through a series of unconfined compressive strength tests. The experimental results show that the incorporation of fibers can increase the compressive strength and residual strength of cement-reinforced clay as well as the corresponding axial strain when the stress peak is reached compared with cement-reinforced clay. The compressive strength of fiber-reinforced cement clay decreases first, then increases with small-composite cement at curing time 14 d and 28 d. However, fiber-reinforced cement clay’s strength increases with the increase of fiber content for heavy-composite cement. The compressive strength of fiber-composite cement-reinforced marine clay increases with the increase of curing time and composite cement content. The growth rate increases with the increase of curing time. The failure mode of composite cement-reinforced clay is brittle failure, while the failure mode of fiber-reinforced cemented clay is plastic failure. Full article

In this study, an experimental approach was developed to analyze and better understand the laser welding and melting of a powder bed process. Different optical diagnostics tools (high-speed camera, infrared camera, pyrometer, etc.) were applied to measure different physical quantities (molten pool morphology, temperature field, residual stresses, and distortions). As a result, measurements during the laser welding process facilitated the building of a database of experimental results (experimental benchmarks). The study of the melting of a powder bed enabled a better understanding of the physics related to the formation and behavior of the molten pool. These results can be used by researchers to improve and validate numerical simulations of these processes. Full article

The compound N-(5-(4-chlorobenzyl)-1,3,5-triazinan-2-ylidene)nitramide (C₁₀H₁₂ClN₅O₂, M = 269.70) was synthesized and structurally confirmed by ¹H NMR, ¹³C NMR, HRMS and single-crystal x-ray diffraction. The crystal belongs to the monoclinic system with space group P2₁/c. The title compound consisted of a benzene ring and a 1,3,5-triazine ring. All carbon atoms in the benzene ring were nearly coplanar with a dihedral (C6–C5–C10 and C7–C8–C9) angle of 1.71°and all non-hydrogen atoms of the 1,3,5-triazine ring were not planar, but exhibited a half-chair conformation. The crystal structure was stabilized by a strong intramolecular hydrogen bonding interaction N(3)–H(3)···O(2) and three intermolecular hydrogen bonding interactions, N(2)–H(2)···O(1), N(2)–H(2)···N(4) and N(3)–H(3)···Cl(1). The preliminary bioassay showed that the title compound showed not only aphicidal activity against Sitobion miscanthi (inhibition rate: 74.1%) and Schizaphis graminum (77.5%), but also antifungal activities against Pythium aphanidermatum (62.0%). These results provide valuable guidelines for the design and synthesis of novel aphid control agents and fungicides. Full article

Curcumin (CR) is a natural antioxidant compound extracted from Curcuma longa (turmeric). Until now, researches related to the incorporation of CR into layered double hydroxides (LDHs) were focused only on hybrid structures based on a MgxAl-LDH matrix. Our studies were extended towards the incorporation of CR in another type of LDH-matrix (Zn3Al-LDH) which could have an even more prolific effect on the antioxidant activity due to the presence of Zn. Four CR-modified Zn3Al-LDH solids were synthesized, e.g., PZn3Al-CR(Aq), PZn3Al-CR(Et), RZn3Al-CR(Aq) and RZn3Al-CR(Et) (molar ratio CR/Al =1/10, where P and R stand for the preparation method (P=precipitation, R=reconstruction), while (Aq) and (Et) indicate the type of CR solution, aqueous or ethanolic, respectively). The samples were characterized by XRD, Attenuated Total Reflectance Fourier Transformed IR (ATR-FTIR) and diffuse reflectance (DR)-UV–Vis techniques and the CR-release was investigated in buffer solutions at different pH values (1, 2, 5, 7 and 8). XRD results indicated a layered structure for PZn3Al-CR(Aq), PZn3Al-CR(Et), RZn3Al-CR(Aq) impurified with ZnO, while RZn3Al-CR(Et) contained ZnO nano-particles as the main crystalline phase. For all samples, CR-release revealed a decreasing tendency towards the pH increase, and higher values were obtained for RZn3Al-CR(Et) and PZn3Al-CR(Et) (e.g., 45% and 25%, respectively at pH 1). Full article

The dynamic behaviour of high-volume fly ash concrete with nano-silica (HVFANS) and polypropylene fibres at curing ages of 7 to 90 days was determined by using a split Hopkinson pressure bar (SHPB) machine. At each curing age, the concrete samples were laboratory tested at different temperatures conditions under strain rates reached up to 101.42 s⁻¹. At room temperature, the results indicated that the dynamic compressive strength of plain concrete (PC) was slightly higher than HVFANS concrete at early curing ages of 7 and 28 days, however, a considerable improvement in the strength of HVFANS concrete was noted at a curing age of 90 days and recorded greater values than PC owing to the increase of fly ash reactivity. At elevated temperatures, the HVFANS concrete revealed a superior behaviour than PC even at early ages in terms of dynamic compressive strength, critical strain, damage and toughness due to increase of nano-silica (NS) activity during the heating process. Furthermore, equations were suggested to estimate the dynamic increase factor (DIF) of both concretes under the investigated factors. Full article

Organic second-order nonlinear optical materials are of great significance in the field of integrated photonics, optical data storage and optical information processing. In this work, two iodide salts with benzo[e]indol cations as electron-withdrawing groups were designed and synthesized, which are (E)-2-(4-hydroxy-3-methoxystyryl)-1,1,3-trimethyl-1H-benzo[e]indol-3-ium iodide (1-TB) and (E)-2-(3,4-dihydroxystyryl)-1,1,3-trimethyl-1H-benzo[e]indol-3-ium iodide (2-TB). Under the irradiation of 1064 nm laser, the second harmonic generations of the 1-TB and 2-TB powders are 760 and 580 times that of urea, respectively. Among them, crystals of 1-TB are successfully grown by a slow cooling method without using seed crystals. Bulk crystal with a size of 8.0 × 3.0 × 1.0 mm³ and many submillimeter single crystals with excellent optical quality are obtained. Full article

In research on enzyme-based biofuel cells, covalent or noncovalent molecular modifications of carbon-based electrode materials are generally used as a method for immobilizing enzymes and/or mediators. However, the influence of these molecular modifications on the electrochemical properties of electrode materials has not been clarified. In this study, we present the electrochemical properties of chemical vapor deposition (CVD)-grown monolayer graphene electrodes before and after molecular modification. The electrochemical properties of graphene electrodes were evaluated by cyclic voltammetry and electrochemical impedance measurements. A covalently modified graphene electrode showed an approximately 25-fold higher charge transfer resistance than before modification. In comparison, the electrochemical properties of a noncovalently modified graphene electrode were not degraded by the modification. Full article