Nonplanar Ring Research Articles

A space-borne ultra-stable laser system with an excellent long-term frequency stability for gravitational wave detection

Abstract Ultra-stable lasers are pivotal in various scientific applications, notably in space gravitational wave detection projects. We develop a space-borne ultra-stable laser system based on a home-made non-planar ring oscillator (NPRO) laser and an ultra-stable cavity laser stabilization system. The ultra-stable cavity is a vertically mounted 8 cm long cavity, with tunable zero-crossing temperature and low vibrational sensitivity. To make a cavity with any standard grade ultra-low expansion glass (ULE) material, and tune the zero-crossing temperature to the satellite platform temperature, we design three ultra-stable cavities with different configurations to unambiguously explore their thermal properties. The measurement results meet the design goals well, and the zero-crossing temperature of the cavity can be tuned from − 19 ∘ C to 16.0 °C. We measure the temperature fluctuation noise through modulation experiment, and it agrees well with the theoretical simulations. The vibrational sensitivities in three directions are measured to be around 10−11 /g–10−10 /g. The total weight of the system is 14.0 kg, with a volume of about 18 L, and the power dissipation of the electrical system is 18.6 W. Finally, the prototype of the space-borne laser shows a frequency instability of 9.5 × 10 − 16 at 0.2 s, and the frequency noise is measured to be 3.6 Hz/Hz1/2 at 6 mHz over three months, satisfying the mission targets of all current space gravitational wave detection programs.

A 2.8 W Single-Frequency Laser Output at 1064 nm from a Gradient-Doped Composite Ceramic Non-Planar Ring Oscillator

A 2.8 W Single-Frequency Laser Output at 1064 nm from a Gradient-Doped Composite Ceramic Non-Planar Ring Oscillator

Exploring the Surface Stability of Non-Benzenoid and Non-Planar High-Membered Rings

The synthesis of carbon-based nanomaterials has experienced an enormous advance in the last 15 years, in part motivated by the advent of On-surface Synthesis (OSS).1 This young field, based on the synthesis of carbon-based nanostructures directly on surfaces thanks to their unique catalytic properties, has allowed the formation of otherwise unattainable extended pi-conjugated systems, like atomically precise graphene nanoribbons,which turned out to be an excellent workbench to explore new physico-chemical properties at the atomic and molecular level.2 Once it was shown the feasibility to use this bottom-up approach to induce organic chemical reactions between tailored precursor monomers, the field evolved toward adding increasing complexity to the final products, either by modifying the dimensionality, edge structure and shape or by including heteroatoms or defects. All these approaches resulted in new intriguing properties as modified band structures or topological states. Of particular recent interest is the effect of non-benzenoid rings in the emergence of pi-magnetism, so far mainly focused on pentagonal rings.3 However, if we want to increase the versatility of the field and explore new possible functionalities associated to the presence of non-benzenoid rings in the nanostructures, it is mandatory to study their stability on surfaces.In this talk, we will discuss the thermal stability of different high-membered non-benzenoid rings, specifically heptagons and octogons, when included into graphene-based nanostructures, paying special attention to the reaction mechanisms involved. References (1) Gourdon, A. On-Surface Covalent Coupling in Ultrahigh Vacuum. Angew. Chem. Int. Ed. 2008, 47 (37), 6950–6953. https://doi.org/10.1002/anie.200802229.(2) Clair, S.; de Oteyza, D. G. Controlling a Chemical Coupling Reaction on a Surface: Tools and Strategies for On-Surface Synthesis. Chem. Rev. 2019, 119 (7), 4717–4776. https://doi.org/10.1021/acs.chemrev.8b00601.(3) Oteyza, D. G. de; Frederiksen, T. Carbon-Based Nanostructures as a Versatile Platform for Tunable π-Magnetism. J. Phys. Condens. Matter 2022, 34 (44), 443001. https://doi.org/10.1088/1361-648X/ac8a7f.

Rare-Earth Metal-Organic Framework with Nonplanar Porphyrin Groups for High-Efficiency Photocatalysis.

Nonplanar porphyrins play crucial roles in many biological processes and chemical reactions as catalysts. However, the preparation of artificial nonplanar porphyrins suffers from complicated organic syntheses. Herein, we present a new rare-earth porphyrinic metal-organic framework (RE-PMOF), BUT-233, which is a three-dimensional (3D) framework structure with the flu topology consisting of 4-connected BBCPPP-Ph ligands H4BBCPPP-Ph = 5',5⁗-(10,20-diphenylporphyrin-5,15-diyl)bis([1,1':3',1″-terphenyl]-4,4'' dicarboxylic acid) and 8-connected Eu6 clusters. Noteworthily, the porphyrin cores of the BBCPPP-Ph ligands in BUT-233 are nonplanar with a ruffle-like conformation. In contrast, the porphyrin core in the free ligand H4BBCPPP-Ph is in a nearly ideally planar conformation, as confirmed by its single-crystal structure. BUT-233 is microporous with 6-8 Å pores and a Brunauer-Emmett-Teller (BET) surface area of 649 m2/g, as well as high stability in common solvents. The MOF was used as a photocatalyst for the oxidation degradation of a chemical warfare agent model molecule CEES (CEES = 2-chloroethyl ethyl sulfide) under the light-emitting diode (LED) irradiation and an O2 atmosphere at room temperature. CEES was almost completely converted into its nontoxic light-oxidized product CEESO (CEESO = 2-chloroethyl ethyl sulfoxide) in only 5 min with t1/2 = 2 min (t1/2: half-life). Moreover, the toxic deep-oxidized product 2-chloroethyl ethyl sulfone (CEESO2) was not detected. The catalytic activity of BUT-233 was high in comparison with those of some previously reported MOF catalysts. The results of photo/electrochemical property studies suggested that the high catalytic activity of BUT-233 was benefited from the presence of nonplanar porphyrin rings on its pore surface.

Narrow‐linewidth injection‐locked Ho:YAG laser by using thulium‐doped fiber laser as pumping source

AbstractWe demonstrated a narrow‐linewidth Ho:yttrium aluminum garnet (YAG) injection‐locked laser by using a 1908 nm thulium‐doped fiber laser as a pumping source to generate 2.09 μm single‐frequency pulses. A compact single‐longitudinal‐mode nonplanar ring oscillator (NPRO) based on Ho:YAG material with a beam quality factor of 1.01 at the central wavelength of 2090.91 nm was considered as the seed source. In the experiment, the pulse energy of 3.6 mJ with a pulse width of 161.6 ns from single‐frequency Ho laser was achieved at a pulse repetition frequency (PRF) of 100 Hz. The linewidth of the single‐frequency pulse spectrum monitored through the heterodyne method was approximately 1.9 MHz at the lowest Ho laser energy.

Strain tuning a Nonplanar Ring Oscillator by 3.5 GHz: Theory and Experiment

Strain tuning a Nonplanar Ring Oscillator by 3.5 GHz: Theory and Experiment

Monolithic VECSEL for stable kHz linewidth.

Vertical-external-cavity surface-emitting semiconductor lasers (VECSELs) are of increasing interest for applications requiring ultra-coherence and/or low noise at novel wavelengths; performance that is currently achieved via high-Q, air-spaced resonators to achieve long intra-cavity photon lifetimes (for the so-called class-A low noise regime), power scaling and high beam quality. Here, we report on the development of a compact, electronically tunable, monolithic-cavity, class-A VECSEL (monolithic VECSEL) for ultra-narrow free-running linewidths. A multi-quantum-well, resonant periodic gain structure with integrated distributed Bragg reflector (DBR) was optically-bonded to an air-gap-free laser resonator created inside a right-angle fused-silica prism to suppress the influence of environmental noise on the external laser oscillation, thus achieving high stability. Mode-hop-free wavelength tuning is performed via the stabilized temperature; or electronically, and with low latency, via a shear piezo-electric transducer mounted on the top of the prism. The free-running linewidth, estimated via the frequency power spectral density (PSD), is sub-kHz over ms timescales and <1.9 kHz for time sampling as long as 1s, demonstrating at least two orders-of-magnitude improvement in noise performance compared to previously reported single frequency VECSELs. The stable, total internal reflection resonator concept is akin to the prevalent monolithic non-planar ring oscillator (NPRO), however the monolithic VECSEL has several important advantages: tailored emission wavelength (via semiconductor bandgap engineering), no relaxation oscillations, no applied magnetic field, and low requirements on the pump beam quality. This approach is power-scalable in principle and could be applied to VECSELs at any of the wavelengths from the visible to the mid-infrared at which they are already available, to create a range of robust, ultra-coherent laser systems with reduced bulkiness and complexity. This is of particular interest for remote metrology and the translation of quantum technologies, such as optical clocks, from research laboratories into real world applications.

Structures and Properties of Planar Ge3O3 Cluster and Its Buckled Honeycomb Two-Dimensional Nanostructure.

The discovery of graphene and its excellent properties inspired the search for more two-dimensional (2D) materials. Understanding the structures and properties of the smallest repeating units as well as crystal 2D materials is helpful for designing 2D materials. As germanium tends to form three-dimensional structures, the preparation of germanium-based 2D nanomaterials is still a challenge. Herein, we report a Ge3O3 cluster with the potential to construct a germanium oxide 2D nanostructure. We conduct a combined anion photoelectron spectroscopy and theoretical study on Ge3O3-/0. The structure of Ge3O3- is a Cs symmetric nonplanar six-membered ring, while that of Ge3O3 is a D3h symmetric planar six-membered ring. Chemical bonding analyses reveal that Ge3O3 exhibits π aromaticity. First-principle results suggest that a buckled honeycomb 2D nanostructure with a wide band gap of 3.14 eV may be produced based on Ge3O3, which is promising in optoelectronic applications especially in blue, violet, and ultraviolet regions.

Synthesis of a new μ-chlorido-bridged tetra-nuclear copper(II) complex containing 2,3,5,6-tetra(2-pyridyl)pyrazine (tppz), chlorido and perchlorato ligands: non-planar central pyrazine rings

A μ-chlorido-bridged tetra-nuclear copper(II) complex containing 2,3,5,6-tetra(2-pyridyl)pyrazine (tppz), chlorido, and perchlorato ligands, starting from 2-aminomethyl pyridine (AMP) and Cu(OAc)2·H2O, was synthesized. The structure of the complex was determined by single-crystal X-ray diffraction (SCXRD), Fourier transform infrared spectroscopy (FT-IR), and electronic absorption spectroscopy (UV–Vis). The redox behavior of the complex was explored by cyclic voltammetry. The tetra-nuclear structure is formed by combining the di-nuclear copper complex of the two tppz ligands with a chloride bridge. The Cu(1) center adopts a distorted octahedral geometry, whereas the other three Cu centers adopt square pyramid geometries. Crystal data of the complex are monoclinic, P21/c, a = 13.602(4) Å, b = 13.438(4) Å, c = 29.412(8) Å, α = 90°, β = 95.258(8)°, γ = 90°, V = 5353(3) Å3, Z = 4. When the SCXRD structure was examined, it was determined that the two central pyrazine rings deviated from planarity, which is one of the four criteria for aromaticity. The aromaticity of the central pyrazine rings, whose planarity is disturbed, is decreased. Based on these bond lengths, the harmonic oscillator aromaticity model (HOMA) values of the non-planar central pyrazine rings were calculated as 0.964926 and 0.942886, respectively.

Unidirectional operation criterion in monolithic nonplanar ring oscillators.

Monolithic nonplanar ring oscillators (NPROs) under an applied magnetic field can operate unidirectional single-frequency lasing due to the loss differences among its four eigenpolarizations, where the minimum was empirically estimated to be 0.01%. However, this value has never been verified because the applied magnetic field is not uniformly distributed, making it hard to resolve both theoretically and experimentally. Here, we propose a method to resolve the applied magnetic field through an NPRO by combining finite-element analysis and experimental verification. By introducing the non-uniform magnetic field information to the eigenpolarization theory, the loss differences can be calculated by path integration along the optical path in the NPRO. The critical point, where the bidirectional lasing is emerging, is identified by the relative amplitude noise (RAN) of the laser and by the beating signal between the clockwise (CW) and counterclockwise (CCW) lasing. With this method, we determine that unidirectional operation is possible with loss differences as low as 0.0001% and 0.0003%, corresponding to two different NPRO designs with out-of-plane angles of 90° and 45°, respectively, which increases the precision of the loss differences for unidirectional single-frequency lasing by more than one order of magnitude. Our findings will greatly facilitate NPRO laser design with lowered magnetic field intensity requirements.

Dual-frequency fundamental-mode NPRO laser for low-noise microwave generation.

Monolithic nonplanar ring oscillators (NPROs) have achieved great success in industry, scientific applications and space missions due to their excellent narrow-linewidth, low-noise, high beam-quality, lightweight and compact performances. Here, we show that stable dual-frequency or multi-frequency fundamental-mode (DFFM or MFFM) laser can be stimulated directly by tunning pump divergence-angle and beam-waist injected to NPRO. The DFFM laser has a frequency deviation of one free spectral range of the resonator and thus can be utilized for pure microwave generation by common-mode-rejection. To demonstrate the purity of the microwave signal, a theoretical phase noise model is established, and the phase noise and the frequency tunability of the microwave signal are experimentally studied. Single sideband phase noise for a 5.7 GHz carrier is measured as low as -112 dBc/Hz at 10 kHz offset, and -150 dBc/Hz at 10 MHz offset in the free running condition of the laser, which outperforms its counterparts from dual-frequency Laguerre-Gaussian (LG) modes. The frequency of the microwave signal can be efficiently tunned through two channels, with frequency tunning coefficients of 15 Hz/V by piezo, and -60.5 kHz/K by temperature, respectively. We expect that such compact, tunable, low-cost and low-noise microwave sources can facilitate multiple applications including miniaturized atomic clocks, communication and radar, etc.

Polarisation compensation in non-planar image-rotating OPO ring resonators.

Non-planar image-rotating OPO ring resonators necessitate polarisation compensation in contrast to their planar counterparts. This is essential for maintaining phase matching conditions for non-linear optical conversion in the resonator during each cavity round trip. In this study, we examine the polarisation compensation and its impact on the performance of two types of non-planar resonators: RISTRA with a π2 image rotation and FIRE with a fractional image rotation (π2 fraction). The RISTRA is insensitive to mirror phase shifts, while the FIRE has a more complex dependence of polarisation rotation on mirror phase shifts. There has been debate over whether a single birefringent element can provide adequate polarisation compensation for non-planar resonators beyond RISTRA-type. Our results show that under certain experimentally feasible conditions, even FIRE resonators can achieve adequate polarisation compensation with a single half-wave plate. We validate our theoretical analysis through numerical simulations and experimental studies of OPO output beam polarisation using ZnGeP2 non-linear crystals.

Isometric Covalent Triazine Framework-Derived Porous Carbons as Metal-Free Electrocatalysts for the Oxygen Reduction Reaction.

Covalent triazine frameworks (CTFs) and their derivative N-doped carbons have attracted much attention for application in energy conversion and storage. However, previous studies have mainly focused on developing new building blocks and optimizing synthetic conditions. The use of isometric building blocks to control the porous structure and to fundamentally understand structure-property relationships have rarely been reported. In this work, two isometric building blocks are used to produce isometric CTFs with controllable pore geometries. The as-prepared CTF with nonplanar hexagonal rings demonstrates higher surface area, larger pore volume, and richer N content than the planar CTF. After pyrolysis, nonplanar porous CTF-derived N-doped carbons exhibit admirable catalytic activity for oxygen reduction in alkaline media (half-wave potential: 0.86 V; Tafel slope: 65 mV dec-1 ), owing to their larger pore volume and the abundance of pyridinic and graphitic N species. When assembled into a zinc-air battery, the as-made electrocatalysts show high capacities of up to 651 mAh g-1 and excellent durability.

1645-nm single-frequency vortex laser from an Er:YAG nonplanar ring oscillator.

A 1645-nm single-frequency vortex beam with narrow linewidth from an Er:YAG nonplanar ring oscillator (NPRO) using an annular pump beam is demonstrated. The pump beam from a 1532-nm fiber laser is shaped to an annular beam by an axicon. The Er:YAG NPRO generates a 1.96-W single-frequency vortex beam under a pump power of 13 W. The linewidth of the 1645-nm vortex laser is measured as 6 kHz. This work provides a convenient way of single-frequency vortex beam generation.

Synthesis, post-functionalization, and photoluminescence of contorted diazaphosphepine-based polycyclic aromatic heterocycles.

Heteroatom-doped organic π-conjugated molecules (OCMs) have become one type of emerging optoelectronic material with intriguing functionalities. Phosphorus (P)-doped OCMs are a special member of heteroatom-doped OCMs where rich P-chemistry is able to fine-tune their optoelectronic properties. Herein, we report a new series of nonplanar diazaphosphepine-based polycyclic aromatic heterocycles (DPP-PAHs). Efficient and mild double P-N cyclization allowed one to readily incorporate two P-centers in DPP-PAHs. With nonplanar diazaphosphepine rings, DPP-PAHs exhibit contorted structures in single crystal structures. The functionalization of double P-centers by H2O2 and S8 gave DPP-PAHs with PO and PS centers, respectively. Compared with the parent small molecule, the DPP-PAHs exhibit high photoluminescence quantum yields. Our experimental and theoretical studies further revealed that both P-environments and conjugated backbones have impacts on the photophysical properties of the DPP-PAHs.

Pharmacophore Mapping Combined with dbCICA Reveal New Structural Features for the Development of Novel Ligands Targeting α4β2 and α7 Nicotinic Acetylcholine Receptors

The neuronal nicotinic acetylcholine receptors (nAChRs) belong to the ligand-gated ion channel (GLIC) group, presenting a crucial role in several biological processes and neuronal disorders. The α4β2 and α7 nAChRs are the most abundant in the central nervous system (CNS), being involved in challenging diseases such as epilepsy, Alzheimer's disease, schizophrenia, and anxiety disorder, as well as alcohol and nicotine dependencies. In addition, in silico-based strategies may contribute to revealing new insights into drug design and virtual screening to find new drug candidates to treat CNS disorders. In this context, the pharmacophore maps were constructed and validated for the orthosteric sites of α4β2 and α7 nAChRs, through a docking-based Comparative Intermolecular Contacts Analysis (dbCICA). In this sense, bioactive ligands were retrieved from the literature for each receptor. A molecular docking protocol was developed for all ligands in both receptors by using GOLD software, considering GoldScore, ChemScore, ASP, and ChemPLP scoring functions. Output GOLD results were post-processed through dbCICA to identify critical contacts involved in protein-ligand interactions. Moreover, Crossminer software was used to construct a pharmacophoric map based on the most well-behaved ligands and negative contacts from the dbCICA model for each receptor. Both pharmacophore maps were validated by using a ROC curve. The results revealed important features for the ligands, such as the presence of hydrophobic regions, a planar ring, and hydrogen bond donor and acceptor atoms for α4β2. Parallelly, a non-planar ring region was identified for α7. These results can enable fragment-based drug design (FBDD) strategies, such as fragment growing, linking, and merging, allowing an increase in the activity of known fragments. Thus, our results can contribute to a further understanding of structural subunits presenting the potential for key ligand-receptor interactions, favoring the search in molecular databases and the design of novel ligands.

Acetophenone-Based 3,4-Dihydropyrimidine-2(1H)-Thione as Potential Inhibitor of Tyrosinase and Ribonucleotide Reductase: Facile Synthesis, Crystal Structure, In-Vitro and In-Silico Investigations

The acetophenone-based 3,4-dihydropyrimidine-2(1H)-thione was synthesized by the reaction of 4-methylpent-3-en-2-one (1), 4-acetyl aniline (2) and potassium thiocyanate. The spectroscopic analysis including: FTIR, 1H-NMR, and single crystal analysis proved the structure of synthesized compound (4), with the six-membered nonplanar ring in envelope conformation. In crystal structure, the intermolecular N-H ⋯ S and C-H ⋯ O hydrogen bonds link the molecule in a two-dimensional manner which is parallel to (010) the plane enclosing R22 (8) and R22 (10) ring motifs. After that, the Hirshfeld surfaces and their related two-dimensional fingerprint plots were used for thorough investigation of intermolecular interactions. According to Hirshfeld surface analysis, the most substantial contributions to the crystal packing are from H ⋯ H (59.5%), H ⋯ S/S ⋯ H (16.1%), and H ⋯ C/C ⋯ H (13.1%) interactions. The electronic properties and stability of the compound were investigated through density functional theory (DFT) studies using B3LYP functional and 6-31G* as a basis set. The compound 4 displayed the high chemical reactivity with chemical softness of 2.48. In comparison to the already reported known tyrosinase inhibitor, the newly synthesized derivatives exhibited almost seven-fold better inhibition of tyrosinase (IC50 = 1.97 μM), which was further supported by molecular docking studies. The compound 4 inside the active pocket of ribonucleotide reductase (RNR) exhibited a binding energy of -19.68 kJ/mol, and with mammalian deoxy ribonucleic acid (DNA) it acts as an effective DNA groove binder with a binding energy of -21.32 kJ/mol. The results suggested further exploration of this compound at molecular level to synthesize more potential leads for the treatment of cancer.

Reprocessable and degradable bio-based polyurethane by molecular design engineering with extraordinary mechanical properties for recycling carbon fiber

In recent years, bio-based covalent adaptable networks (CANs) and vitrimers have developed rapidly in order to meet the renewable and sustainable requirements. It should be emphasized that the performance of the network need be upgraded and optimized to substitute petroleum-based polymers. Herein, a series of high-performance bio-based polyurethane were synthesized containing castor oil, isosorbide, vanillin derivative and 4,4′-Dicyclohexylmethane diisocyanate. By fine-tuning the bio-based diols, the hydrogen bond distribution and the crosslink density of the network were adjustable. The thermal mechanical properties and stress relaxation properties of the bio-based polyurethane were optimized. The bio-based polyurethane CANs shows tensile strength of 38.1 MPa, elongation at break of 243% and toughness of 55.7 MJ m −3 , which is outstanding among most reported bio-based CANs. In addition, the polymer has excellent water resistance, shape memory and re-deformability. Due to the dissociation of imine bonds under mild acid conditions, the carbon fiber composite can readily degrade in mixed solvent for 3 h at 60 °C and the properties of recycled carbon fibers are highly preserved. Fabrication of extraordinary mechanical properties, reprocessably, and degradable polyurethanes through network structure design. • Nonplanar rigid ring of isosorbide brings extraordinary mechanical properties to bio-based polyurethane CANs. • Adjusting the ratio of diols can tune the degree of cross-linking and distribution of hydrogen bonds in the networks. • Isosorbide can also improve fluidity of the network and lower activation energy. • CF composites can be chemically degraded under mild conditions for non-destructive recycling of CF.

Alternate method to measure transmission and internal losses in non-planar ring oscillator laser

The transmission T and internal losses L of a non-planar ring oscillator (NPRO) laser are measured using a unique approach. Measurement of slope efficiency, axial mode separation, and relaxation oscillation frequency as a function of NPRO output power are all used in this procedure. T was assessed to be 2.3%, which was significantly higher than the supplier’s given value of 1.7% for a 32-deg angle of incidence at the NPRO output coupler at 1064 nm. The estimated value of internal loss was 4.2%.

Substituted piperidine as a novel lead molecule for the treatment of Parkinson's disease: Synthesis, crystal structure, hirshfeld surface analysis, and molecular modeling

The current research outlines the synthesis of benzyl 4- (4-chlorophenylamino) -1-(4-chlorophenyl) -2,6-bis(4-chlorophenyl) -1,2,5,6-tetrahydropyridine -3-carboxylate. The title compound was crystallized in the monoclinic space group P21/n with Z = 4 and unit cell parameters a = 13.6684 Å (8), b = 9.1256 Å (4), c = 14.0839 Å (8), = 111.168 (7)°, and V = 1638.18 (17)°. The six-membered non-planar ring is shaped like a boat. Intermolecular C–H···Cl hydrogen bonds connect molecules in a three-dimensional crystal framework. The most significant contributions to crystal packing, according to the Hirshfeld surface investigation of the crystal structure, are from H ··· H (35.3%), H... Cl/Cl... H (27.0%), and H ··· C/C ··· H (21.8%). As a result, van der Waals interactions take precedence in crystal packing. In-vitro studies suggested this compound has better IC50 value of 0.588 ± 0.09 µM against MAO-A. In silico investigations, such as molecular docking, demonstrated that this molecule possessed exceptionally high Monoamine Oxidase A and Monoamine Oxidase B activity, with a binding energy value of -32.504 kJ/mol. Furthermore, Density functional theory (DFT) analyses supported these findings and suggested derivative 4 as a potential 'lead' molecule in pharmaceutical discovery and development.