The benefits of transitioning to chemical and material circularity are readily apparent. However, identifying and developing the necessary chemical transformations for platform chemical recycling is a significant challenge. Alcohols are an important industrial platform class owing to existing demand and the potential for their renewable supply through the utilization of biomass processing waste streams. Acceptorless Dehydrogenation (AD) is a critical process in the context of circularity, particularly in the transformation of alcohols. This mini-review offers an in-depth examination of both homogeneous and heterogeneous catalytic processes used in acceptorless dehydrogenation. We primarily concentrate on two sustainable feedstocks, glycerol and ethanol. Through the assessment and juxtaposition of homogenous and heterogeneous catalysts in the context of the alcoholysis of glycerol and ethanol, we aim to establish a comparison based on activity, longevity, and the green chemistry metrics associated with the catalytic processes (specifically the E-factor; energy economy coefficient, epsilon; and environmental energy impact factor, xi). We established evaluation criteria using the matrics to provide a means for comparison among homogeneous and heterogeneous catalysts and help identify promising catalyst classes that can be further developed. This review seeks to shed light on the existing constraints that must be addressed to advance the development of catalysts that are more efficient, cost-effective, and resilient for AD reactions.
Pentosan polysulfate sodium (PPS) is an orphan drug with anticoagulant activity. PPS is prepared from the chemical processing of xylan extracted from beechwood tree to yield a mixture of 4–6 kDa polysaccharides. The chain is mainly composed of sulfated xylose (Xyl) with branched 4-O-methyl-glucuronate (MGA). During generic drug development, the quality attributes (QAs) including monosaccharide composition, modification, and length need to be comparable to those found in the reference list drug (RLD). However, the range of QA variation of the RLD PPS has not been well characterized. Here, multiple PPS RLD lots were studied using quantitative NMR (qNMR) and diffusion ordered spectroscopy (DOSY) to quantitate the components in the mixture and to probe both inter- and intra-lot precision variability. The DOSY precision assessed using coefficient of variation (CV) was 6
Protein higher order structure (HOS) including the oligomer distribution can be critical for efficacy, safety and stability of drug products (DP). Oligomerization is particularly relevant to chemically modified protein therapeutics that have an extended pharmacokinetics profile. Therefore, the direct assessment of protein oligomerization in drug formulation is desired for quality assurance and control. Here, two non-invasive methods, dynamic light scattering (DLS) and diffusion ordered spectroscopy (DOSY) NMR, were applied to measure translational diffusion coefficients (Ddls and Dnmr) of proteins in formulated drug products. The hydrodynamic molecular weights (MWhd), similar to hydrodynamic size, of protein therapeutics were derived based on a log(Ddls) vs log(MWhd) correlation model established using protein standards. An exponent value of -0.40 ± 0.01 was established for DLS measured log(D) vs. log(MWhd) using protein standards and a theoretical exponent value of -0.6 was used for unstructured polyethylene glycol (PEG) chains. The analysis of DLS derived MWhd of the primary species showed the fatty acid linked glucagon-like peptide 1 (GLP-1) was in different oligomer states, but the fatty acid linked insulin and PEG linked proteins were in monomer states. Nevertheless, equilibrium and exchange between oligomers in formulations were universal and clearly evidenced from DOSY-NMR for all drugs except peginterferon alfa-2a. The correlation models of log(D) vs. log(MWhd) could be a quick and efficient way to predict MWhd of protein, which directly informs on the state of protein folding and oligomerization in formulation.
The electronic effects of supports on immobilized organometallic complexes impact their activity and lifetime, yet remain poorly understood. Here we describe a systematic study of the support effects experienced by an organometallic complex immobilized on doped hydrotalcite-like materials. To that end, we describe the synthesis and characterization of the first organometallic species immobilized on a palette of doped hydrotalcites via sulfonate linkers. The organometallic species consists of iridium N-heterocyclic carbene (NHC) carbonyl complex ([Na][Ir-(NHC-Ph-SO3)2(CO)2]), a highly active molecular catalyst for transfer hydrogenation of glycerol. The hydrotalcite supports are composed of Al, Mg, and a compatible transition-metal dopant (Fe, Cu, Ni, Zn). The materials were characterized extensively by STEM, XPS, TGA, PXRD, FT-IR, N2 desorption, ICP-AES, TPD, and microcalorimetry to probe the morphology and electronic properties of the support and elucidate structure-property relationships.
Objective: The study aimed to investigate the effects of intraoperative dexmedetomidine on postoperative sleep disturbance for different surgical patients and compare such effects between different dose of dexmedetomidine. Methods: A total of 7418 patients undergoing nine types of non-cardiac major surgeries were retrospectively studied. Patients were separated into DEX (dexmedetomidine) or Non-DEX (Non-dexmedetomidine) groups based on the use of dexmedetomidine during surgery. The patients who reported they could not fall asleep during the night or woke up repeatedly during the most of the night at the day of the surgery and whose NRS were >6 were defined as cases with severe sleep disturbance. Propensity score matched analysis based on all preoperative baseline data was performed along with logistic regression analysis including different surgery types and dosage of dexmedetomidine use. Results: In both of the unmatched cohort (OR, 0.49 [95% CI: 0.43-0.56]) and matched cohort (0.49 [95% CI: 0.42-0.58]), the DEX group had a significantly lower incidence of severe sleep disturbance than the Non-DEX group. In the subgroup analysis, for gynecological and urological surgery population, the ORs for DEX-group reached 0.21 (95% CI, 0.13-0.33; P<0.0001) and 0.30 (95% CI,0.19-0.47; P<0.0001), respectively. In addition, low-dose dexmedetomidine (0.2-0.4 mu g.kg(-1).h(-1)) showed the greatest effect with an odds ratio of 0.38 (95% CI: 0.31-0.44; P< 0.0001), and the incidence of severe sleep disturbance in the low-dose group was significantly lower (11.5% vs. 17.7% vs. 16.5%, P<0.0001) than that in the medium- (0.4-0.6 mu g.kg(-1).h(-1)) and high-dose (0.6-0.8 mu g.kg(-1).h(-1)) groups. Conclusion: Intraoperative dexmedetomidine use can significantly decrease the incidence of severe sleep disturbance on the day of surgery for patients undergoing non-cardiac major surgery, and the effects were most significant in patients receiving gynecological and urological surgery. Furthermore, low-dose dexmedetomidine (0.2-0.4 mu g.kg(-1).h(-1)) is most effective for prevention of postoperative sleep disturbance.
Background Postoperative depression is one of the most common mental disorders in patients undergoing cancer surgery and it often delays postoperative recovery. We investigated whether dezocine, an analgesic with inhibitory effect on the serotonin and norepinephrine reuptake, could relieve postoperative depressive symptoms in patients undergoing colorectal cancer surgery. Methods This randomized, controlled, single-center, double-blind trial was performed in the Second Affiliated Hospital of the Army Medical University. A total of 120 patients were randomly assigned to receive either sufentanil (1.3 μg/kg) with dezocine (1 mg/kg) (dezocine group; n=60) or only sufentanil (2.3 μg/kg) (control group; n=60) for patient-controlled intravenous analgesia after colorectal cancer surgery. The primary outcome was the Beck Depression Inventory score at 2 days after surgery. The secondary outcomes included the Beck Anxiety Inventory, sleep quality, and quality of recovery scores. Results Compared with those in the control group, patients in the dezocine group had lower depression scores (7.3±3.4 vs. 9.9±3.5, mean difference 2.6, 95% CI: 1.43.9; P<0.001) at 2 days after surgery and better night sleep quality at the day of surgery (P=0.010) and at 1 day after the surgery (P<0.001). No significant difference was found in other outcomes between the two groups. Conclusions Intravenous analgesia using dezocine can relieve postoperative depression symptoms and improve sleep quality in patients undergoing colorectal cancer surgery.
Thermally-robust and water-soluble Ir(i) and Ir(iii) N-heterocyclic carbene complexes with sulfonate functionalized wingtips are prolific catalysts for carbonate transfer hydrogenation from glycerol without additives in aqueous media.
The upgrading of biomass derivatives to biofuels and chemicals through transfer hydrogenation (TH) is attractive relative to direct hydrogenation, especially when the hydrogen donors can be sourced renewably. Here we report the first process that uses glycerol, a renewable waste material from biodiesel processing, as a hydrogen donor in the catalytic TH of a biomass-derived platform chemical, levulinic acid, to selectively afford γ-hydroxyvaleric acid (GHV) and lactic acid (LA). GHV can be further converted to γ-valerolactone (GVL), a widely used platform chemical. Levulinic acid can be used directly, without esterification, which is typically needed for transfer hydrogenation. The process is efficiently facilitated by robust iridium N-heterocyclic carbene (NHC) complexes with sulfonate functional groups at low catalyst loading (1–10 ppm), affording quantitative conversion of levulinic acid in the presence of KOH to GHV, with >100,000 TON in 2 h at 150 °C, using 1 ppm catalyst. The most prolific catalyst, [(NHC-SO3-)2(CO)2Ir]Na, can also facilitate transfer hydrogenation from other hydrogen donors, such as 2-propanol, potassium formate, and most notably, ethanol, which can also be derived from renewables. Ethanol is a highly efficient hydrogen donor for levulinic acid using this catalyst, affording >7,000 turnovers in 2 h using 10 ppm catalyst.
Breast cancer is the most commonly diagnosed malignant tumor in women. Perioperative anesthesia and analgesia management are closely related to postoperative rehabilitation, and may even be associated with long-term prognosis. The current review summarizes the literature about the effects of thoracic paravertebral nerve block (TPVB) on the perioperative period of breast cancer. TPVB is able to reduce the consumption of opioids and general anesthetics during breast cancer surgery and relieve acute pain after surgery, improve postoperative immunosuppression and tumor microenvironment, and boost anti-tumor potential, which all facilitate rapid rehabilitation. However, the impact of TPVB on the incidence of chronic postsurgical pain (CPSP) requires more researches. Therefore, the application of TPVB in the perioperative period of breast cancer is worthy of promotion. Further investigations are required to explore the impact of TPVB for the long-term prognosis of breast cancer. Key words: Thoracic paravertebral nerve block; Breast cancer; Tumor microenvironment; Long-term prognosis; Chronic postsurgical pain
We propose a low complexity channel equalization algorithm. A complete real-time OFDM system was built for evaluation. The EVM value of 16-QAM signal constellation is improved by 28 dB in OBTB case. The received optical power was below than −12.5dBm with a BER of 3.8E−3.
以Al2O3为载体,采用浸渍法制备了Pt、Co、Cu、Ni/Al2O3 4种不同活性组分的催化剂(N/Al2O3),进一步研究了已制备的催化剂对丙三醇水蒸气重整制氢性能的影响,然后通过添加金属氧化物改变Pt/Al2O3催化剂的性能,提高催化剂的活性、稳定性和抗积碳性能,并对催化剂进行了TPR、BET表征.实验结果表明,Pt-Li2O/Al2O3催化剂适用于丙三醇水重整制氢反应,并表现出较好的活性和抗积碳性能.
The transfer hydrogenation of CO2 from glycerol to afford formic and lactic acid is a highly attractive path to valorizing two waste streams and is a significantly more thermodynamically favorable process than direct CO2 hydrogenation. We report the first homogeneous catalyst for this transformation consisting of a water-soluble Ru N-heterocyclic carbene complex. The catalyst affords lactic and formic acid selectively in the presence of a base at temperatures between 150 and 225 °C. Carbonate salts can also be utilized in place of CO2, affording the same products at higher rates.
Stonehenge-like PbI2nanostructure, preparedviasolvent substitution, provides important progress for scalable fabrication and highly efficient perovskite solar cells.
We present a finite impulse response (FIR) filter by using field programmable gate array (FPGA). It is designed in MATLAB, and we get filter coefficient from it. The implementation results showed decent performance in filtering.
In this work, we report experimental results regarding the recycling of optical pumps signal for energy conversion, namely optical pumps from Raman amplifiers and fiber optic parametric amplifiers. Therefore, we propose the usage of optical signals to power remotely located network elements. After propagation over 25 km single mode fiber an electrical power of 0.9 mW and 18.1 mW was attained for the Raman amplifier and fiber optic parametric amplifier, respectively.