A Cubic Tinkertoy-like Heterometallic Cluster with a Record Magnetocaloric Effect.

Clusters showing a giant magnetocaloric effect (MCE) are of interest as molecular coolants for magnetic refrigeration. Herein, we report two heterometallic clusters, denoted as Gd152Ni14@Cl24 and Sm152Ni8, just to highlight their inorganic core motifs, obtained by ligand-controlled co-hydrolysis of Ni2+ and Ln3+ (Ln = Gd, Sm) in the presence of N-(2-hydroxyethyl)iminodiacetic acid (H2HEIDA). Both clusters display fascinating cubic Tinkertoy-like structures, with the core motifs being built of multiple metallic shells of Platonic and Archimedean polyhedra. The isothermal magnetic entropy change─a direct measurement of MCE─was determined to be 52.65 J·kg-1·K-1 at 2.5 K and 7.0 T for the Gd-containing cluster; this value is the highest known for any molecular clusters so far reported.

Coherent detection of the rotational Doppler effect measurement based on triple Fourier transform.

In recent years, the rotational Doppler effect (RDE) has been widely used in rotational motion measurement. However, the performance of existing detection systems based on the RDE are generally limited by the drastic reduction of signal-to-noise ratio (SNR) due to the influence of atmospheric turbulence, partial obscuration of the vortex beam (VB) during propagation, and misalignment between the optical axis of VB and the rotational axis of the object, which poses a challenge for practical applications. In this paper, we proposed a coherent detection method of the RDE measurement based on triple Fourier transform. First, the weak RDE signal in backscattered light is amplified by using the balanced homodyne detection method, and the amplified signal still retains the same characteristic of severe broadening in the frequency domain as the original signal. Furthermore, we proposed the triple Fourier transform to extract the broadened RDE frequency shift signal after the coherent amplification. The proposed method significantly improves the SNR of RDE measurement and facilitates the accurate extraction of rotational speed, which helps to further improve the RDE detection range and promote its practical application.

Substituent Positioning Effects on the Magnetic Properties of Sandwich-Type Erbium(III) Complexes with Bis(trimethylsilyl)-Substituted Cyclooctatetraenyl Ligands.

Lanthanide complexes with judiciously designed ligands have been extensively studied for their potential applications as single-molecule magnets. With the influence of ligands on their magnetic properties generally established, recent research has unearthed certain effects inherent to site differentiation due to the different types and varying numbers of substituents on the same ligand platform. Using two new sandwich-type Er(III) complexes with cyclooctatetraenyl (COT) ligands featuring two differently positioned trimethylsilyl (TMS) substituents, namely, [Li(DME)Er(COT1,5-TMS2)2]n (Er1) and [Na(DME)3][Er(COT1,3-TMS2)2] (Er2) [COT1,3-TMS2 and COT1,5-TMS2 donate 1,3- and 1,5-bis(trimethylsilyl)-substituted cyclooctatetraenyl ligands, respectively; DME = 1,2-dimethoxyethane], and with reference to previously reported [Li(DME)3][Er(COT1,4-TMS2)2] (A) and [K(DME)2][Er(COT1,4-TMS2)2] (B), any possible substituent position effects have been explored for the first time. The rearrangement of the TMS substituents from the starting COT1,4-TMS2 to COT1,3-TMS2 and COT1,5-TMS2, by way of formal migration of the TMS group, was thermally induced in the case of Er1, while for the formation of Er2, the use of Na+ in the placement of its Li+ and K+ congeners is essential. Both Er1 and Er2 display single-molecule magnetic behaviors with energy barriers of 170(3) and 172(6) K, respectively. Magnetic hysteresis loops, butterfly-shaped for Er1 and wide open for Er2, were observed up to 12 K for Er1 and 13 K for Er2. Studies of magnetic dynamics reveal the different pathways for relaxation of magnetization below 10 K, mainly by the Raman process for Er1 and by quantum tunneling of magnetization for Er2, leading to the order of magnitude difference in magnetic relaxation times and sharply different magnetic hysteresis loops.

Lanthanide-Based Molecular Magnetic Semiconductors.

Magnetic semiconductors, with integrated properties of ferromagnets and semiconductors, are significant for developing next-generation spintronic devices. Herein two atomically precise clusters of dysprosium(III) tellurides, formulated respectively as [Na2(15-crown-5)3(py)][(η5-Cp*Dy)5(Te)6](py)4 (Dy5Te6, Cp* = pentamethylcyclopentadienyl; py = pyridine) and [K(2,2,2-cryptand)]2[(η5-Cp*Dy)6(Te3)(Te2)2(Te)3] (Dy6Te10), are reported. Crystallographic studies revealed the presence of multifarious tellurido ligands within the polyhedral cluster cores. Spectroscopic and magnetic studies showed that both clusters are single-molecule magnets exhibiting slow magnetic relaxation behaviors at low temperatures and semiconductors with optical bandgaps comparable to benchmark semiconductors. These clusters represent probably the first lanthanide-based molecular magnetic semiconductors.

Analysis of rotational Doppler shift with multi-ring vortex beams.

Vortex beams (VBs) with orbital angular momentum have shown great potential in the detection of transverse rotational motion of spatial targets which is undetectable in the classical radar scheme. However, most of the reported rotational Doppler measurements based on VBs can only be realized under ideal experimental conditions. The long-range detection is still a challenge. The detection distance based on rotational Doppler effect (RDE) is mainly limited by the scattered signal's signal-to-noise ratio (SNR). In this work, we investigated the influence of multi-ring vortex beams (MVBs) on the rotational Doppler frequency spectrum of scattered light from an object based on RDE and proposed a method of SNR enhancement of RDE signal. Firstly, different types of MVBs composed of a set of single-ring VBs with the same topological charge and different radii are designed, including multi-ring Laguerre Gaussian beam (MLGB), multi-ring perfect vortex beams (MPVB), and high-order Laguerre Gaussian beam (HLGB). Then, the influence of the number of rings and radial radius interval on the intensity profiles of MVBs and rotational Doppler frequency spectra under aligned and misaligned conditions is studied in detail. And the reasons why different types of MVBs lead to different SNR enhancement effectiveness with the increase of rings are also analyzed theoretically. Finally, proof-of-concept experiments were conducted to verify the effectiveness of the SNR enhancement method for RDE signals. The results showed that the amplitudes of the Doppler spectra generated by the MLGB and MPVB are improved substantially with the increase of rings, but the enhancement effect caused by the former is superior to the latter. The gain of HLGB on the RDE signal is the lowest. This study provides a useful reference for the optimization of rotational Doppler detection systems and may be of great application value in telemetry, long-range communication and optical imaging.

Detection of a spinning object using a superimposed optical vortex array.

The optical vortex (OV) carries unique orbital angular momentum (OAM) and experiences a Doppler frequency shift when backscattered from a spinning object. This rotational Doppler effect (RDE) has provided a solution for the non-contact detection of rotating motion. The reported RDE researches mainly use a single OV that generates frequency shifts proportional to its topological charge and has low robustness to light incidence. Here, we show the distinctive RDE of superimposed optical vortex array (SOVA). We analyze the holistic OAM of SOVA which is represented in terms of a superposition of azimuthal harmonics and displays a unique modal gathering effect. In the experiment of RDE, the frequency shift signals of SOVA show a precise mapping to the OAM modes and the modal gathering effect contributes to enhance the amplitude of signals, which has the potential to enhance robustness against non-coaxial incidence. This finding provides a new aspect of RDE and a pioneered example for introducing various SOVAs into rotation detection.

Determinative Effect of Axial Linearity on Single-Molecule Magnet Performance in Dinuclear Dysprosium Complexes.

Two dichloride-bridged dinuclear dysprosium(III) complexes based on salen ligands, namely, [Dy(L1 )(µ-Cl)(thf)]2 (1; H2 L1 =N,N'-bis(3,5-di-tert-butylsalicylidene)phenylenediamine) and [Dy2 (L2 )2 (µ-Cl)2 (thf)2 ]2 (2; H2 L2 =N,N'-bis(3,5-di-tert-butylsalicylidene)ethylenediamine) are reported. These two complexes have two short Dy-O(PhO) bonds that exhibit angles of ∼90° for 1 and ∼143° for 2, leading to clear slow relaxation of the magnetization for 2 and not for 1. Compound 2 has a near-identical core to the recently reported compound [Dy2 (L3 )2 (µ-Cl)2 (thf)2 ] (3; H2 L3 =N-(2-pyridylmethyl)-N,N-bis(2'-hydroxy-3',5'-di-tert-butylbenzyl)amine). The only substantial difference is the relative angle of the two O(PhO) -Dy-O(PhO) vectors, which is collinear in 2 owing to inversion symmetry and ∼68° in 3 due to a molecular C2 axis. It is shown that this subtle structural difference leads to large differences in the dipolar ground states, giving rise to open magnetic hysteresis for 3 and not for 2.

Electron Paramagnetic Resonance Spectra of Pentagonal Bipyramidal Gadolinium Complexes.

Gadolinium is a special case in spectroscopy because of the near isotropic nature of the 4f7 configuration of the +3 oxidation state. Gd3+ complexes have been studied in several symmetries to understand the underlying mechanisms of the ground state splitting. The abundance of information in Gd3+ spectra can be used as a probe for properties of the other rare earth ions in the same complexes. In this work, the zero-field splitting (ZFS) of a series of Gd3+ pentagonal bipyramidal complexes of the form [GdX1X2(Leq)5]n+ [n = 1, X = axial ligands: Cl-, -OtBu, -OArF5 or n = 3, X = tBuPO(NHiPr)2, Leq = equatorial ligand: Py, THF or H2O] with near fivefold symmetry axes along X1-Gd-X2 was investigated. The ZFS parameters were determined by fitting of room-temperature continuous wave electron paramagnetic resonance (EPR) spectra (at X-, K-, and Q-band) to a spin Hamiltonian incorporating extended Stevens operators compatible with C5 symmetry. Examination of the acquired parameters led to the conclusion that the ZFS is dominated by the B20 term and that the magnitude of B20 is almost entirely dependent on, and inversely proportional to, the donor strength of the axial ligands. Surveying the continuous shape measure and the X1-Gd-X2 angle of the complexes showed that there is some correlation between the proximity of each complex to D5h symmetry and the magnitude of the B65 parameter, but that the deformation of the X1-Gd-X2 angle is more significant than other distortions. Finally, the magnitude of B20 was found to be inversely proportional to the thermal barrier for the reversal of the magnetic moment (Ueff) of the corresponding isostructural Dy3+ complexes.

SUMO1 and Defective Spermatozoa Correlate with Endogenous Hydrogen Peroxide and Live Birth Outcome in Intrauterine Insemination Cycles for Unexplained Infertility.

This study aimed to investigate the correlation between hydrogen peroxide (H2O2), small ubiquitin-like modifier molecules (SUMO), and pregnancy outcomes in couples with unexplained infertility (UI) undergoing intrauterine insemination (IUI) treatment. We prospectively collected semen samples from 56 couples with UI and divided the spermatozoa into motile and immotile fractions by density gradient centrifugation (DSC). Immunofluorescence staining was used to examine the immunostaining and localization of nuclear pore complex (NPC), SUMO1, and SUMO2/3 in spermatozoa. We detected H2O2 levels by chemiluminescence methods. We found that H2O2 levels correlated with NPC (neck) (r = 0.400) and NPC (tail) (r = 0.473) in motile sperm fractions. In immotile fractions, H2O2 positively correlated with NPC (tail) (r = 0.431) and SUMO1 (neck) (r = 0.282). Furthermore, the positive NPC (tail) group had a significantly lower live birth rate than the negative NPC group (17.9% = 5/28 vs. 42.9% = 12/28). In conclusion, H2O2 positively correlated with SUMO1 (neck) and NPC (tail) in human spermatozoa. The DSC may partially eliminate defective spermatozoa (positive NPC staining); however, if defective spermatozoa remain in the motile fraction, this scenario is associated with a low live birth rate following IUI treatment.

Sensory root demyelination: Transforming touch into pain.

The normal feeling of touch is vital for nearly every aspect of our daily life. However, touching is not always felt as touch, but also abnormally as pain under numerous diseased conditions. For either mechanistic understanding of the faithful feeling of touch or clinical management of chronic pain, there is an essential need to thoroughly dissect the neuropathological changes that lead to painful touch or tactile allodynia and their corresponding cellular and molecular underpinnings. In recent years, we have seen remarkable progress in our understanding of the neural circuits for painful touch, with an increasing emphasis on the upstream roles of non-neuronal cells. As a highly specialized form of axon ensheathment by glial cells in jawed vertebrates, myelin sheaths not only mediate their outstanding neural functions via saltatory impulse propagation of temporal and spatial precision, but also support long-term neuronal/axonal integrity via metabolic and neurotrophic coupling. Therefore, myelinopathies have been implicated in diverse neuropsychiatric diseases, which are traditionally recognized as a result of the dysfunctions of neural circuits. However, whether myelinopathies can transform touch into pain remains a long-standing question. By summarizing and reframing the fragmentary but accumulating evidence so far, the present review indicates that sensory root demyelination represents a hitherto underappreciated neuropathological change for most neuropathic conditions of painful touch and offers an insightful window into faithful tactile sensation as well as a potential therapeutic target for intractable painful touch.

Fragmental optical vortex for the detection of rotating object based on the rotational Doppler effect.

Rotational Doppler effect (RDE), as a counterpart of the conventional linear Doppler effect in the rotating frame, has attracted increasing attention in recent years on rotational object detection. Many previous works have investigated the RDE based on the whole optical vortex field. In this work, we report on the RDE of the partially obstructed optical vortex and the corresponding rotational speed extraction method. Based on the orbital angular momentum (OAM) mode analysis theory, we establish the relationship between the OAM spectrum and the RDE frequency shift of fragmental optical vortex (FOV). The mechanism of the rotational speed extraction is analysed and validated by the numerical simulation and experiments. Further, a dual Fourier transformation method is proposed to accurately obtain the rotational speed which successfully overcomes the problem of the discrete distribution of the RDE signals. Our work may be useful for practical remote sensing based on the optical RDE metrology.

Rotational object detection at noncoaxial light incidence based on the rotational Doppler effect.

The rotational Doppler effect (RDE) of optical vortex which can be used to detect the rotation speed, has become a well-known phenomenon and a hot topic of research in recent years. However, because the beam axis must be coaxial with the rotational axis of the object, it can only be used to detect cooperative targets in practical application. Here, we provide a novel approach for measuring rotational speed under light non-coaxial incidence relative to the rotating axis that uses the adjacent frequency difference of rotational Doppler shift signals. Theoretically, the rotational Doppler shift is proportional to the OAM mode of the incident beam, and the nature of the OAM carried by each photon is a discrete or quantized quantity under off-axis conditions leading to the discrete distribution of the Doppler shift signals. Experimentally, by extracting the difference between two adjacent Doppler shift signals, the rotating speed of the object can be determined. Based on our method, the rotational speed of the object can be measured precisely without the pre-known information about the position of the rotating axis. Our work supplies a significant complement to the conventional RDE theory and we believe it may promote the realistic application of the optical RDE-based metrology.

Detection of a spinning object with circular procession using an optical vortex beam.

The rotational Doppler effect (RDE) provides an efficient way to measure rotational frequency using an optical vortex beam. Crucially, most research based on the RDE just involves a spinning object or a spinning object coupled with a longitudinal velocity along the beam propagation. We analyze the interaction mechanism between optical orbital angular momentum and a spinning object with circular procession and experimentally demonstrate simultaneous measurements of two rotational frequencies. This technique broadens application of the RDE in optical metrology and remote detection of targets with micro-motions.

Studies of the Temperature Dependence of the Structure and Magnetism of a Hexagonal-Bipyramidal Dysprosium(III) Single-Molecule Magnet.

The hexagonal-bipyramidal lanthanide(III) complex [Dy(OtBu)Cl(18-C-6)][BPh4] (1; 18-C-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane ether) displays an energy barrier for magnetization reversal (Ueff) of ca. 1000 K in a zero direct-current field. Temperature-dependent X-ray diffraction studies of 1 down to 30 K reveal bending of the Cl-Ln-OtBu angle at low temperature. Using ab initio calculations, we show that significant bending of the O-Dy-Cl angle upon cooling from 273 to 100 K leads to a ca. 10% decrease in the energy of the excited electronic states. A thorough exploration of the temperature and field dependencies of the magnetic relaxation rate reveals that magnetic relaxation is dictated by five mechanisms in different regimes: Orbach, Raman-I, quantum tunnelling of magnetization, and Raman-II, in addition to the observation of a phonon bottleneck effect.

Locating the center of rotation of a planar object using an optical vortex.

The rotational Doppler effect (RDE) of optical vortex beams provides an efficient way to measure the rotational frequency of objects based on rotational Doppler frequency shifts, while the frequency shift signals display a distinct broadening effect when the vortex beam is laterally misaligned with the center of rotation of a planar object. We use a modal decomposition method to reveal the broadening effect and obtain a linear fitting equation between the quantity of signals and lateral misalignments. In an experiment of RDE, the lateral misalignment is extracted from the quantity of signal peaks. The fitting equation is proved to be precise within the uncertainty of ±0.17mm (±2.8% of the vortex beam radius), and the center of rotation is located with an error less than 3.33% of the beam radius. Our work provides a new approach to locate the center of rotation of noncooperative objects, which may be valuable in mechanical manufacturing and optical noncontact metrology.

Representation of In-Service Performance for Cable-Stayed Railway-Highway Combined Bridges Based on Train-Induced Response's Sensing Data and Knowledge.

Real-time representation of the current performance of structures is an important task for perceiving potential danger in in-service bridges. Methods driven by the multisource sensing data of structural health monitoring systems are an effective way to achieve this goal. Due to the explicit zero-point of signals, the live load-induced response has an inherent advantage for quantitatively representing the performance of bridges. Taking a long-span cable-stayed railway-highway combined bridge as the case study, this paper presents a representation method of in-service performance. First, the non-stationary sections of train-induced response are automatically extracted by wavelet transform and window with threshold. Then, the data of the feature parameter of each non-stationary section are automatically divided into four cases of train load according to the calculational theory of bridge vibration under train effect and clustering analysis. Finally, the performance indexes for structural deformation and dynamics are determined separately, based on hierarchical clustering and statistical modeling. Fusing the real variability of massive data from monitoring and the knowledge of mechanics of theoretical calculations, accurate and robust indexes of bridge deflection distribution and forced vibration frequency are obtained in real time. The whole process verifies the feasibility of the representation of bridge in-service performance from massive multisource sensing data. The presented method, framework, and analysis results can be used as a reference for the design, operation, and maintenance works of long-span railway bridges.

Ligand Fluorination to Mitigate the Raman Relaxation of DyIII Single-Molecule Magnets: A Combined Terahertz, Far-IR and Vibronic Barrier Model Study.

The fast Raman relaxation process via a virtual energy level has become a puzzle for how to chemically engineer single-molecule magnets (SMMs) with better performance. Here, we use the trifluoromethyl group to systematically substitute the methyl groups in the axial position of the parent bis-butoxide pentapyridyl dysprosium(III) SMM. The resulting complexes-[Dy(OLA )2 py5 ][BPh4 ] (LA =CH(CF3 )2 - 1, CH2 CF3 - 2, CMe2 CF3 - 3)-show progressively enhanced TB hys (@100 Oe s-1 ) from 17 K (for 3), 20 K (for 2) to 23 K (for 1). By experimentally identifying the varied under barrier relaxation energy in the 5-500 cm-1 regime, we are able to identify that the C-F bond related vibration energy of the axial ligand ranging from 200 to 350 cm-1 is the key variant for this improvement. Thus, this finding not only reveals a correlation between the structure and the Raman process but also provides a paradigm for how to apply the vibronic barrier model to analyze multi-phonon relaxation processes in lanthanide SMMs.

Generating a new type of polygonal perfect optical vortex.

We generate a new type of perfect optical vortex called the polygonal perfect optical vortex (PPOV) by combining the Bessel-Gauss beam with the high-order cross-phase (HOCP) at the plane of a spatial light modulator (SLM). This is the first time that the HOCP is applied to the Fourier plane of an optical field (POV) instead of directly acting on an optical field itself. Experimentally, the symmetrical PPOV is generated, and the capability of asymmetric distribution is demonstrated. Furthermore, we discuss the influence of parameters on a PPOV. On this basis, we show a novel function of the PPOV that can adjust the energy distribution at the vertices while maintaining the orbital angular momentum as much as possible, which facilitates applications in optical micro-manipulation.

Analysis of misaligned optical rotational Doppler effect by modal decomposition.

The optical rotational Doppler effect (RDE) is closely related to the unique orbital angular momentum (OAM) carried by optical vortex, whose topological charge means the mode of OAM. Compared with the coaxial incidence, the rotational Doppler frequency shift spectrum of a misaligned optical vortex (misaligned RDE) widens according to a certain law. In this paper, an OAM modal decomposition method of the misaligned optical RDE is proposed and the relative intensity of different OAM modes, namely the OAM spectrum, is derived based on an inner product computation. Analyses show that lateral displacements and angular deflections change the distribution of OAM modes relative to the rotation axis of the object. A misaligned Laguerre-Gaussian (LG) vortex can be represented as a specific combination of coaxial LG modes, and the difference between the topological charge of two adjacent modes is 1 or 2 with lateral displacements or angular deflections respectively. An experiment of misaligned optical RDE using a superimposed LG vortex is executed, and the obtained frequency shift spectrum with misaligned incidence expands into a set of discrete signals, which agrees well with the theoretical results. Moreover, we can get the rotation frequency of the object from an expanded frequency spectrum more quickly and accurately based on the difference between two adjacent signal peaks. The proposed method contributes to analyze the misaligned optical RDE comprehensively, which is significant in remote sensing and optical metrology.

Rotational Doppler effect detection by LG beams with a nonzero radial index.

The capability to detect the rotational speed of non-cooperative targets in a long distance is a difficult problem to be solved. In recent years, vortex light provides a feasible solution for the measurement of rotational speed for its spiral phase and the orbital angular momentum. Laguerre-Gaussian (LG) mode, as the typical vortex beam, has been widely employed in rotational Doppler effect (RDE) experiments. Here, we show that the nonzero radial index LG beam not only has a specific physical meaning but also can enhance the light intensity and the amplitude of RDE frequency signal relative to a zero radial index LG beam. To this end, we theoretically analyze the reason of intensity enhancement of a nonzero radial index beam and verify the conclusion in a variable control experiment. Our study provides a new aspect of LG beams that can be considered in rotational speed detection based on RDE. It may produce an improvement of the detection range of rotating targets in practical applications.