Visualizing molecular weights differences in supramolecular polymers.

Issues of molecular weight determination have been central to the development of supramolecular polymer chemistry. Whereas relationships between concentration and optical features are established for well-behaved absorptive and emissive species, for most supramolecular polymeric systems no simple correlation exists between optical performance and number-average molecular weight (Mn). As such, the Mn of supramolecular polymers have to be inferred from various measurements. Herein, we report an anion-responsive supramolecular polymer [M1·Zn(OTf)2]n that exhibits monotonic changes in the fluorescence color as a function of Mn Based on theoretical estimates, the calculated average degree of polymerization (DPcal) increases from 16.9 to 84.5 as the monomer concentration increases from 0.08 mM to 2.00 mM. Meanwhile, the fluorescent colors of M1 + Zn(OTf)2 solutions were found to pass from green to yellow and to orange, corresponding to a red shift in the maximum emission band (λmax ). Therefore, a relationship between DPcal and λmax could be established. Additionally, the anion-responsive nature of the present system meant that the extent of supramolecular polymerization could be regulated by introducing anions, with the resulting change in Mn being readily monitored via changes in the fluorescent emission features.

2 × 4†kW near-single-mode laser output assisted by an optimized bidirectional oscillating-amplifying integrated fiber laser configuration.

Bidirectional output oscillating-amplifying integrated fiber laser (B-OAIFL) can achieve the two-ports laser amplification based on a single cavity, showcasing a promising prospect. In order to improve both the laser power and beam quality, we first simulate and optimize the stimulated Raman scattering (SRS) effect in the B-OAIFL. The simulation results show the SRS effect can be suppressed by optimizing the diameter as well as the length of the active fiber at different locations. With the guidance of theoretical and experimental analysis for the combined suppression of SRS and transverse mode instability (TMI), a near-single-mode B-OAIFL with 2 × 4 kW was demonstrated. Based on this foundation, we further devoted ourselves to the pursuit of the optimization of the structure and performance. The necessity of the configuration of side pump, which was initially introduced for its exceptional performance in stabilizing temporal chaos, was reevaluated in detail. With its negative impacts on efficiency improvement and SRS suppression were analyzed and verified, we removed this configuration and finally demonstrated a more simplified design with superior performance. A total bidirectional output of 8105 W was achieved, with an O-O efficiency of 79.6% and a near-single-mode beam quality of M A 2∼1.36,M B 2∼1.63. No signs of TMI were observed, and the signal-to-SRS suppression ratio was over 38 dB. The results still demonstrate a promising potential for power scaling based on this configuration and parameters.

Effective mitigation of photodarkening-induced transverse mode instability in a monolithic fiber laser oscillator by 450†nm laser irradiation.

The photodarkening (PD) and transverse mode instability (TMI) effects are two main factors limiting the power increase and long-term stability of high-power fiber lasers. A prolonged burn-in test for an all-fiber laser oscillator below the TMI threshold was carried out. We observed the PD-induced TMI effects, which manifested as a sudden decrease in the output power due to higher-order mode leakage. After several minutes of exposure to a high-power density 450 nm laser diode (LD), the output power returned to its initial state, significantly enhancing the oscillator's stability. The 450 nm LD probably mitigates the accumulation of thermal effects by inhibiting the photodarkening effect, thus preventing the occurrence of the TMI effects and improving the stability of the oscillator's output power. Our work provides useful guidance for the development of high-stability fiber laser oscillators.

Origin of SRS-induced beam quality distortion under TMI threshold.

In high power fiber lasers, the degradation of beam quality caused by Raman effect has attracted more and more attention in recent years, but its physical mechanism is still unclear. We're going to differentiate between heat effect and nonlinear effect by duty cycle operation. The evolution of beam quality at different pump duty cycles has been studied based on a quasi-continuous wave (QCW) fiber laser. It is found that even if the Stokes intensity is only -6 dB (energy proportion: 26%) lower than that of the signal light intensity, the beam quality has no obvious change with the duty cycle of 5%; on the contrary, when the duty cycle gradually approaches 100% (CW-pumped scheme), the beam quality distortion changes faster and faster with the increase of Stokes intensity. The experimental results are contrary to core-pumped Raman effect theory [IEEE Photon. Technol. Lett.34, 215 (2022)10.1109/LPT.2022.3148999], and further analysis confirms that the heat accumulation in the process of Stokes frequency shift should be responsible for this phenomenon. That is the first time, to the best of our knowledge, for intuitive reveal of the origin of stimulated Raman scattering (SRS)-induced beam quality distortion under transverse mode instability (TMI) threshold in an experiment.

Towards a tapered Yb-doped fiber-based narrow linewidth single-mode fiber laser with a high signal to Raman ratio.

We demonstrate an all-fiber high-power narrow-linewidth fiber laser based on a homemade tapered Yb-doped fiber (T-YDF). The laser performance is investigated and systematically compared with different seed powers and pump manners. The experimental results reveal that the injected seed power requires a trade-off designed to take into account the impact of spectral broadening, nonlinear effects, and transverse mode instability (TMI). Compared with the co-pump manner, the counter-pump manner performs well in inhibiting nonlinearities, spectral broadening, and improving the TMI threshold. Under the counter-pump manner, this narrow-linewidth T-YDF amplifier realized a 2.09 kW output power with a 3 dB spectral linewidth of ∼0.34 nm, a beam quality of M2∼1.28 and a high Raman suppression ratio over 53.5 dB, the highest reported power for such a T-YDF-based narrow-linewidth single-mode laser, to the best of our knowledge. This work provides a promising pathway towards implementing monolithic high-power narrow-linewidth single-mode fiber lasers.

Demonstration of 3kW × 2 ports bidirectional output oscillating-amplifying integrated fiber laser employing chirped and tilted fiber Bragg gratings for co-SRS suppression.

Bidirectional output oscillating-amplifying integrated fiber laser (B-OAIFL) is a newly developed configuration with many advantages like compactness and good reliability. In this work, a B-OAIFL with a low time-stabilized threshold was constructed by employing a pair of side pump/signal combiner in the oscillating section, which demonstrates smooth temporal characteristics with no pulse detected by the photodetector at the output power level of only a few of tens Watts. We investigated the effect of side pumping on the Raman Stokes light and verified its contribution to mitigating the temporal-chaos-induced stimulated Raman scattering (SRS). The phenomenon of co-SRS caused by the mutual excitation of backward Stokes light from two amplifying sections under bidirectional pumping was first reported and studied. A pair of chirped and tilted fiber Bragg gratings (CTFBGs) were applied between the oscillating and amplifying sections to suppress the co-SRS, and the effect of the number of CTFBGs on the suppression of co-SRS was studied in detail experimentally. Finally, we successfully suppressed the co-SRS, and achieved a 3kW × 2 ports laser output, with a near-single-mode beam quality of M A 2∼1.3,M B 2∼1.4. In contrast, without the use of CTFBG, only a 2 kW-level output was obtained from each port, limited by co-SRS (with an SRS suppression ratio of less than 15 dB). The maximum output power of end A and end B is 3133 W and 3213 W, with the SRS suppression ratio of about 27.6 dB and 28.1 dB, respectively. No TMI features were observed under bidirectional pumping. The results demonstrate a significant potential for further power scaling based on this configuration. To the best of our knowledge, it is the highest output power achieved based on the B-OAIFL.

Annotating functional effects of non-coding variants in neuropsychiatric cell types by deep transfer learning.

Genomewide association studies (GWAS) have identified a large number of loci associated with neuropsychiatric traits, however, understanding the molecular mechanisms underlying these loci remains difficult. To help prioritize causal variants and interpret their functions, computational methods have been developed to predict regulatory effects of non-coding variants. An emerging approach to variant annotation is deep learning models that predict regulatory functions from DNA sequences alone. While such models have been trained on large publicly available dataset such as ENCODE, neuropsychiatric trait-related cell types are under-represented in these datasets, thus there is an urgent need of better tools and resources to annotate variant functions in such cellular contexts. To fill this gap, we collected a large collection of neurodevelopment-related cell/tissue types, and trained deep Convolutional Neural Networks (ResNet) using such data. Furthermore, our model, called MetaChrom, borrows information from public epigenomic consortium to improve the accuracy via transfer learning. We show that MetaChrom is substantially better in predicting experimentally determined chromatin accessibility variants than popular variant annotation tools such as CADD and delta-SVM. By combining GWAS data with MetaChrom predictions, we prioritized 31 SNPs for Schizophrenia, suggesting potential risk genes and the biological contexts where they act. In summary, MetaChrom provides functional annotations of any DNA variants in the neuro-development context and the general method of MetaChrom can also be extended to other disease-related cell or tissue types.

A genetically defined disease model reveals that urothelial cells can initiate divergent bladder cancer phenotypes.

Small cell carcinoma of the bladder (SCCB) is a rare and lethal phenotype of bladder cancer. The pathogenesis and molecular features are unknown. Here, we established a genetically engineered SCCB model and a cohort of patient SCCB and urothelial carcinoma samples to characterize molecular similarities and differences between bladder cancer phenotypes. We demonstrate that SCCB shares a urothelial origin with other bladder cancer phenotypes by showing that urothelial cells driven by a set of defined oncogenic factors give rise to a mixture of tumor phenotypes, including small cell carcinoma, urothelial carcinoma, and squamous cell carcinoma. Tumor-derived single-cell clones also give rise to both SCCB and urothelial carcinoma in xenografts. Despite this shared urothelial origin, clinical SCCB samples have a distinct transcriptional profile and a unique transcriptional regulatory network. Using the transcriptional profile from our cohort, we identified cell surface proteins (CSPs) associated with the SCCB phenotype. We found that the majority of SCCB samples have PD-L1 expression in both tumor cells and tumor-infiltrating lymphocytes, suggesting that immune checkpoint inhibitors could be a treatment option for SCCB. We further demonstrate that our genetically engineered tumor model is a representative tool for investigating CSPs in SCCB by showing that it shares a similar a CSP profile with clinical samples and expresses SCCB-up-regulated CSPs at both the mRNA and protein levels. Our findings reveal distinct molecular features of SCCB and provide a transcriptional dataset and a preclinical model for further investigating SCCB biology.

Demonstration of constant-cladding tapered-core Yb-doped fiber for mitigating thermally-induced mode instability in high-power monolithic fiber amplifiers.

In this work, a large-mode-area (LMA) step-index constant-cladding tapered-core (CCTC) Yb-doped fiber with a cladding diameter of ∼600 µm is successfully fabricated. The CCTC fiber has a small-core region (diameter of ∼20 µm) at both ends and a large-core region (diameter of ∼36 µm) in the middle. To prove the laser performance of the CCTC fiber, a detailed comparison experiment with conventional uniform fiber with the same effective core diameter is carried out in a multi-kW all-fiber MOPA configuration. The experimental results show that employing the CCTC fiber can effectively mitigate the thermally-induced transverse mode instability (TMI) in both co-pump and counter-pump schemes, and realize high slope efficiency and single-mode beam quality (M2∼1.30). Under the counter-pump scheme, the TMI threshold of the CCTC fiber is observed at ∼2.49 kW with a slope efficiency of 86.2%, while the uniform fiber amplifier exhibits a TMI threshold of ∼2.05 kW. The theoretical analysis based on a semi-analytical model indicates this CCTC fiber can effectively improve the TMI threshold owing to a stronger gain saturation. Our results verify the great potential of such an LMA CCTC fiber to mitigate thermal-induced TMI effect and achieve single-mode operation without sacrifice of laser efficiency in high power monolithic fiber lasers, and the further power scaling is expected by optimizing the fiber design.

Kilowatt random Raman fiber laser with full-open cavity.

Random Raman fiber laser (RRFL) has been widely studied in high-power laser generation due to its special lasing characteristics. However, all previous high-power results are based on the half-open cavity. In this letter, we demonstrate an applicable high-power RRFL with the simplest structure, that is, a full-open cavity. The lasing dynamic and output characteristics are theoretically and experimentally studied. Laser source with multi-longitudinal modes can result in the random laser output from one side even in the full-open cavity. The ratio of the backward output power is mainly determined by the reflectivity of fiber ends. The experimental results show that such a simple structure can easily generate kilowatts of random laser power and is a promising setup to achieve higher output power, which is also an important platform to study the laser dynamic in high-power full-open cavity without any point-action or regular distributed reflectors.

2 × 2†kW near-single-mode bidirectional high-power output from a single-cavity monolithic fiber laser.

Traditional monolithic fiber lasers can only achieve unidirectional high-power laser output. In this Letter, a novel high-power linear cavity fiber laser that can achieve bidirectional high-power output is proposed and demonstrated. In an ordinary laser resonant cavity, we replace the high-reflectivity fiber Bragg grating with a low-reflectivity fiber Bragg grating to realize bidirectional laser output. In our experiment, the laser cavity was composed of two fiber Bragg gratings with a reflectivity of about 10%. The pump power provided by the 976 nm laser diodes was injected into a double-clad Yb-doped fiber with core/cladding diameters of 20/400 µm. At the maximum pump power, the bidirectional output powers were 2025 W and 1948 W, respectively, and the output laser beam quality (M2 factor) at both ends was about 1.5. For the first time, to the best of our knowledge, the feasibility of a bidirectional output fiber laser that can achieve double high (2-kW-level) power was verified. Compared with a traditional unidirectional output laser, this type of bidirectional output laser can achieve a double high-power laser by employing a laser resonant cavity. Thus, the average cost and structure size can be further reduced in mass production.

Simple method for high average power supercontinuum generation based on Raman mode locking in a quasi-CW fiber laser oscillator.

A simple generation method for a supercontinuum (SC) based on Raman mode locking (RML) in a quasi-continuous wave (QCW) fiber laser oscillator is demonstrated experimentally and analyzed in this paper. The power of the SC is adjustable by changing the pump repetition rate and duty cycle. Under the pump repetition rate of 1 kHz and duty cycle of 11.5%, an SC output with a spectral range of 1000-1500 nm is obtained at a maximum output power of 791 W. The RML is fully analyzed in terms of the spectral and temporal dynamics. RML plays a major role in this process and further enriches the generation of the SC. To the best of the authors' knowledge, this is the first report on directly generating a high and adjustable average power SC using a large-mode-area (LMA)-based oscillator, which provides a proof-of-concept experiment for achieving a high average power SC source and greatly improves the potential application value of the SC source.

Tapered Yb-doped fiber enabled a 4†kW near-single-mode monolithic fiber amplifier.

In this Letter, we demonstrate a monolithic high-power master oscillator power amplifier by using a home-made double-clad tapered Yb-doped fiber (T-YDF) with an input end of ∼20/400 µm and an output end of ∼30/600 µm. Thanks to perfect core/cladding matching with the fiber components at both ends of the T-YDF, the laser is pumped bidirectionally and an output power of over 4 kW with a high slope efficiency of 84.1% and excellent beam quality M2 ∼ 1.46 is achieved. In contrast to previous work on common fiber lasers, experimental results also reveal that the co-pump scheme has a higher transverse mode instability (TMI) threshold and power-boosting capability than that of a counter-pump scheme. To the best of our knowledge, this is the highest output power demonstrated to date from such a T-YDF with excellent beam quality. This work indicates the great potential of the T-YDF to realize further power scaling, high laser efficiency, and excellent beam quality in high-power fiber lasers.

Radiofrequency ablation for liver tumors abutting complex blood vessel structures: treatment protocol optimization using response surface method and computer modeling.

OBJECTIVE: To achieve a result of a large tumor ablation volume with minimal thermal damage to the surrounding blood vessels by designing a few clinically-adjustable operating parameters in radiofrequency ablation (RFA) for liver tumors abutting complex vascular structures. METHODS: Response surface method (RSM) was employed to correlate the ablated tumor volume (Ra) and thermal damage to blood vessels (Dt) based on RFA operating parameters: ablation time, electrode position, and insertion angle. A coupled electric-thermal-fluid RFA computer model was created as the testbed for RSM to simulate RFA process. Then, an optimal RFA protocol for the two conflicting goals, namely (1) large tumor ablation and (2) small thermal damage to the surrounding blood vessels, has been achieved under a specific ablation environment. RESULTS: Linear regression analysis confirmed that the RFA protocol significantly affected Ra and Dt (the adjusted coefficient of determination Radj2 = 93.61% and 95.03%, respectively). For a proposed liver tumor scenario (liver tumor with a dimension of 4×3×2.9 cm3 abutting a complex vascular structure), an optimized RFA protocol was found based on the regression results in RSM. Compared with a reference RFA protocol, in which the electrode was centered in the tumor with a 12-min ablation time, the optimized RFA protocol has increased Ra  from 98.1% to 99.6% and decreased Dt from 4.1% to 0.4%, achieving nearly the complete ablation of proposed liver tumor and ignorable thermal damages to vessels. CONCLUSION: This work showed that it is possible to design a few clinically-adjustable operating parameters of RFA for achieving a large tumor ablation volume while minimizing thermal damage to the surrounding blood vessels.

High-peak-power pump-modulated quasi-CW fiber laser.

Quasi-continuous wave (CW) laser output with high peak power and high energy is preferred in some industrial applications. Due to the non-linear effects and transverse mode instability, such high-peak-power laser output is difficult to achieve via monolithic fiber lasers in CW mode. For diode-pumped monolithic fiber lasers, by applying overshoot pulse modulation to the pumping diodes, we obtain a pulse laser output with a peak power much higher than that in CW mode. In this paper, it has been theoretically studied that stable pulses with the width of µs level can be generated with quasi-CW operation without distortion according to our simulation. We also experimentally demonstrate a bi-directional pumped quasi-CW monolithic fiber laser operating in CW and pulse modes. In quasi-CW mode, by applying overshoot pulse modulation to the diodes, with a frequency of 1 kHz and a pulse width of 100 µs, the peak power of the output laser reached 9713 W with an average power of 898 W and M2 of 2.4 and 2.3 in the two orthogonal directions, respectively. To the best of our knowledge, this is the very first quasi-CW fiber laser of a 10-kW level with the M2 level of 2.

Wide temperature operation of kilowatt fiber oscillators.

To meet the requirements of fiber laser applications under extreme temperatures or when there is a large temperature difference, it is necessary to develop fiber lasers able to operate in a wide temperature range. At present, there is a lack of reports on high-power fiber lasers that can operate in a wide temperature range with low power fluctuations. Thus, we designed a 1 kW fiber oscillator that can operate in a wide temperature range through temperature-related rate equations. The output characteristics of the oscillator are measured in the operating temperature range from -30∘C to 20°C. The experimental results show that the laser output power fluctuates by 7% over the entire temperature range. It was discovered that as the ambient temperature decreased, the efficiency of the laser decreased, and this issue is discussed in detail. This work has guiding significance for the design of high-power fiber lasers operating at a wide temperature range, and simultaneously, to the best of our knowledge, it provides the first kilowatt fiber oscillator that can operate in a wide temperature range between -30∘C and 20°C.

Water compatible supramolecular polymers: recent progress.

Water compatible supramolecular polymers (WCSPs) combine aqueous compatibility with the reversibility and environmental responsiveness of supramolecular polymers. WCSPs have seen application across a number of fields, including stimuli-responsive materials, healable materials, and drug delivery, and are attracting increasing attention from the design, synthesis, and materials perspectives. In this review, we summarize the chemistry of WCSPs from 2016 to mid-2021. For the sake of discussion, we divide WCSPs into five categories based on the core supramolecular approaches at play, namely hydrogen-bonding arrays, electrostatic interactions, large π-conjugated subunits, host-guest interactions, and peptide-based systems, respectively. We discuss both synthesis and polymer structure, as well as the underlying design expectations. The goal of this overview is to deepen our understanding of the strategies that have been exploited to prepare WCSPs, as well as their properties and uses. Thus, a section devoted to potential applications is included in this review.

AIEgen-Enabled Multicolor Visualization for the Formation of Supramolecular Polymer Networks.

Extensive reports on the use of supramolecular polymer networks (SPNs) in self-healing materials, controlled release system and degradable products have led more researchers to tap their potential owing to the unique properties. Yet, the attendant efforts in the visualization through conventional luminescence methods during the formation of SPNs have been met with limited success. Herein, we designed a special type of SPNs prepared by PPMU polymer chains containing pyrene benzohydrazonate (PBHZ) molecules as AIEgens for the multicolor visualization with naked eyes. The complete detection of the formation process of the networks relied on the PBHZ molecules with aggregation-induced ratiometric emission (AIRE) effect, which enabled the fluorescence of the polymer networks transits from blue to cyan, and then to green with the increasing crosslinking degree derived from the hydrogen bonds between 2-ureido-4-pyrimidone (UPy) units of the polymer chains. Additionally, we certificated the stimuli-responsiveness of the obtained SPNs, and the fluorescence change, as well as observing the morphology transition. The AIEgen-enabled multicolor visualization of the formation of SPNs may provide better understanding of the details of the crosslinking interactions in the microstructural evolution, giving more inspiration for the multifunctional products based on SPNs.

A Strategy Based on Aggregation-Induced Ratiometric Emission to Differentiate Molecular Weight of Supramolecular Polymers.

Molecular weight has an important bearing on the properties of supramolecular polymers. However, the intuitive differentiation of the molecular weight of supramolecular polymers remains challenging. Given this situation, establishing a reliable relationship between fluorescence properties and molecular weight may be a promising strategy. Herein, we prepared a supramolecular monomer M1 with aggregation-induced ratiometric emission characteristics. With the increasing M1 concentration (0.100-100 mM), the average degree of polymerization (DPDOSY ) rose from 1.00 to 293. Meanwhile, the color changed from dark blue to cyan, finally to yellow-green in the same concentration range. Hence, the intuitive relationship between DPDOSY and fluorescence colors was constructed, allowing the visual differentiation of molecular weight. Moreover, the fluorescence color could be regulated by introducing a competitive molecule to induce the depolymerization of supramolecular polymers.

Unlocking Chemically Encrypted Information Using Three Types of External Stimuli.

Encryption is critical to information security; however, existing chemical-based information encryption strategies are still in their infancy. We report here a new approach to chemical encryption involving a supramolecular gel QR (quick response) code with multiple encryption functions. Three color "turn-on" supramolecular polymer gels, G1-G3, were prepared that produce pink, purple, and yellow colors when subject to treatment with acetic acid vapor, UV light, and methanolic FeCl3, respectively. As the result of hydrogen-bonding interactions at the gel interfaces, the three gels can be assembled to produce gel G4. Engraving a QR code pattern onto G4 then gave gel G5. When one or two stimuli are applied to the individual pieces corresponding to the QR engraved versions of the gels G1-G3 making up G5, a complete scannable pattern is not displayed, and the stored information cannot be recognized. Only when three different stimuli are applied at the same time does G5 give a complete recognizable pattern allowing the stored information to be retrieved. This strategy was applied to the decryption-based opening of a coded lock.