J-Aggregate Promoting NIR-II Emission for Fluorescence/Photoacoustic Imaging-Guided Phototherapy.

J-aggregate is a promising strategy to enhance second near-infrared window (NIR-II) emission, while the controlled synthesis of J-aggregated NIR-II dyes is a huge challenge because of the lack of molecular design principle. Herein, bulk spiro[fluorene-9,9'-xanthene] functionalized benzobisthiadiazole-based NIR-II dyes (named BSFX-BBT and OSFX-BBT) are synthesized with different alkyl chains. The weak repulsion interaction between the donor and acceptor units and the S…N secondary interactions make the dyes to adopt a co-planar molecular conformation and display a peak absorption >880 nm in solution.

Planar-structured thiadiazoloquinoxaline-based NIR-II dye for tumor phototheranostics.

Second near-infrared (NIR-II) fluorescence imaging shows huge application prospects in clinical disease diagnosis and surgical navigation, while it is still a big challenge to exploit high performance NIR-II dyes with long-wavelength absorption and high fluorescence quantum yield. Herein, based on planar π-conjugated donor-acceptor-donor systems, three NIR-II dyes (TP-DBBT, TP-TQ1, and TP-TQ2) were synthesized with bulk steric hindrance, and the influence of acceptor engineering on absorption/emission wavelengths, fluorescence efficiency and photothermal properties was systematically investigated. Compared with TP-DBBT and TP-TQ2, the TP-TQ1 based on 6,7-diphenyl-[1,2,5]thiadiazoloquinoxaline can well balance absorption/emission wavelengths, NIR-II fluorescence brightness and photothermal effects.

Achieving cinnamic acid amides in water by a variant of acyltransferase from Mycobacterium smegmatis and its immobilized form using Ni-NTA modified aspen powder as a carrier.

An aqueous N-acylation reaction for preparing cinnamic acid amides was realized by using a variant of acyltransferase from Mycobacterium smegmatis (MsAcT-L12A), whereas the wild-type MsAcT showed no activity. MsAcT-L12A exhibited broad substrate adaptability, and preferred the substrates with electron-donating group. When the vinyl cinnamate (1a, 40 mM) and p-methoxyaniline (2a, 4 mM) were involved in the reaction, the excellent yield reached to 86.

Semi-rational engineering an aldo-keto reductase for stereocomplementary reduction of α-keto amide compounds.

Enantio-pure α-hydroxy amides are valuable intermediates for the synthesis of chiral pharmaceuticals. The asymmetric reduction of α-keto amides to generate chiral α-hydroxy amides is a difficult and challenging task in biocatalysis. In this study, iolS, an aldo-keto reductase from Bacillus subtilis 168 was exhibited as a potential biocatalyst, which could catalyze the reduction of diaryl α-keto amide such as 2-oxo-N, 2-diphenyl-acetamide (ONDPA) with moderate S-selectivity (76.

Revisiting molecularly conformation-planarized organic dyes for NIR-II fluorescence imaging.

Fluorescence imaging in the second window (NIR-II, 1000-1700 nm) provides deeper penetration depth and higher resolution, but there is still a dilemma for designing NIR-II dyes for simultaneously enhancing fluorescence efficiency and prolonging excitation wavelength. Herein, a molecular conformation planarization strategy has been revisited to guide the synthesis of two donor-acceptor-donor dyes (named T-BBT and BT-BBT). On the one hand, conformational planarization can extend the absorption peaks of T-BBT and BT-BBT to the NIR region with high molar extinction coefficients of 30.

Engineering silica encapsulated composite of acyltransferase from Mycobacterium smegmatis and MIL-88A: A stability-and activity-improved biocatalyst for N-acylation reactions in water.

Here the metal-organic framework material MIL-88A is used to purify and immobilize an acyltransferase from Mycobacterium smegmatis (MsAcT) simultaneously from the broken bacterial liquid. Regarding the possibility that the MsAcT@MIL-88A may display weak stability in its application, a silica layer is further introduced around it as a "shield" to protect the enzyme from degradation. The obtained MsAcT@MIL-88A@silica can exhibit high activity recovery, excellent thermal, pH, and storage stabilities compared with those of MsAcT@MIL-88A.

2-Arachidonoylglycerol Attenuates Myocardial Fibrosis in Diabetic Mice Via the TGF-β1/Smad Pathway.

Purpose: Diabetic cardiomyopathy (DM) is the cause of late cardiac dysfunction in diabetic patients. Myocardial fibrosis is the main pathological mechanism, and it is associated with transforming growth factor-β1(TGF-β1) expression up-regulation. 2-Arachidonoylglycerol (2-AG) is an endogenous cannabinoid that can effectively improve myocardial cell energy metabolism and cardiac function.

Asymmetric Synthesis of Spiro[3,2'-morpholine-oxindoles] Derivatives via the [5 + 1] Annulation Reaction.

An efficacious method in which BINOL-type chiral imidodiphosphoric acid catalyzed the asymmetric [5 + 1] annulation reaction of 2-pyrrolylphenol with 1-methylindoline-2,3-dione was established. The strategy tolerated a broad substrate scope, and 30 examples were obtained. A range of enantioenriched spiro[3,2'-morpholine-oxindole] derivatives which incorporate a tertiary stereocenter, with moderate to excellent yields (up to 96%) and enantioselectivities (up to 99%) under mild conditions, was delivered.

Transmuscular quadratus lumborum block versus oblique subcostal transversus abdominis plane block for analgesia in laparoscopic hysterectomy: a randomised single-blind trial.

Objective: The transmuscular quadratus lumborum (TQL) block and the oblique subcostal transversus abdominis plane (OSTAP) block both contribute to multimodal analgesia after laparoscopic surgery. The objective of this study was to compare the analgesic effects of the TQL block versus OSTAP block after laparoscopic hysterectomy.

Design: Prospective single-centre randomised single-blind trial.

Comparison of the effect of different volumes ropivacaine on deep serratus anterior plane block in patients undergoing breast surgery: a prospective randomized double-blinded trial.

Background: A larger volume of local anesthetic provides a wider range of blocked sensory but carries a greater risk. The purpose of this trial was to compare the effect of different volumes of ropivacaine injected to deep serratus anterior plane in patients undergoing breast surgery.

Methods: In this randomized double-blind trial, 60 patients undergoing breast surgery were randomly allocated to R10, R20 and R30 groups (n=20), and received deep serratus anterior plane block with 10, 20 and 30 mL of 0.

Effects of Ropivacaine Concentration on Analgesia After Ultrasound-Guided Serratus Anterior Plane Block: A Randomized Double-Blind Trial.

Purpose: Serratus anterior plane (SAP) block is effective for analgesia after breast surgery. Whether a higher local anesthetic concentration prolongs sensory block duration and improves postoperative analgesia remains unclear. The aim of this study was to compare the analgesic effects of SAP block with different concentrations of ropivacaine.

Rational enhancement of enzyme-catalyzed enantioselective reaction by construction of recombinant enzymes based on additive strategy.

A rational enhancement of kinetic resolution process for producing (S)-N-(2-ethyl-6-methylphenyl) alanine from racemic methyl ester using lipase B from Candida antarctica (CalB) was investigated. With the benefit results that lipase CalB-catalyzed reactions can be effectively regulated using amino acids (such as histidine and lysine) as additives, CalBs modified (mCalBs) by n-histidines at the N terminal and n-lysines at the C terminal were constructed and expressed. The results show that both soluble and precipitated mCalBs can effectively catalyze the hydrolysis reaction without adding any extra additives.

Directly covalent immobilization of Candida antarctica lipase B on oxidized aspen powder by introducing poly‑lysines: An economical approach to improve enzyme performance.

In our previous study, we could achieve high soluble expression of Candida antarctica lipase B (CalB) in E. coli by fusion poly‑amino acid tags on CalB (pCalB). Herein, we are surprised to find that pCalB can be easily and directly covalent binding on a simply oxidized aspen powder (OAP) by the aid of poly‑lysine tags.

Functionalized Poplar Powder as a Support Material for Immobilization of Enoate Reductase and a Cofactor Regeneration System.

In this study, functionalized poplar powder (FPP) was used as a support material for the immobilization of enoate reductase (ER) and glucose-6-phosphate dehydrogenase (GDH) by covalent binding. Under optimal conditions, the immobilization efficiency of ER-FPP and GDH-FPP was 95.1% and 84.

Stereoselective synthesis of a key chiral intermediate of (S)-Rivastigmine by AKR-GDH recombinant whole cells.

Herein, three aldo/ketoreductases (AKRs) were obtained and used to prepare N- ethyl-methyl-carbamic acid-3-[(1S)-hydroxy-ethyl]-phenyl ester ((S)-NEMCA-HEPE), which is a key intermediate of (S)-Rivastigmine. To avoid the usage of extra cofactors, the recombinant whole-cells containing AKRs and glucose dehydrogenase (GDH) were constructed and applied in the reduction reaction. The excellent conversion of 83.

Co-immobilization of enoate reductase with a cofactor-recycling partner enzyme.

Herein we established co-immobilized methods for enoate reductases (ERs) and glucose dehydrogenase (GDH), forming a cofactor regeneration system. In cross-linked enzyme aggregates (CLEAs), ammonium sulfate and oxidized dextran were selected as a precipitant and a cross-linker, respectively. In biomimetic immobilization (BI), ER-GDH-silica particles (ER-GDH-SPs) were rapidly formed through a one-step approach by using a silicic acid precursor.

Simultaneously achieve soluble expression and biomimetic immobilization of Candida antarctica lipase B by introducing polyamine tags.

Polyamine tags fused in Candida antarctica lipase B (CalB) can help achieve high soluble expression of CalB in E. coli and can directly mediate silicification, which leads to rapid formation of a CalB-silica particle complex through a one-step approach. After optimization experiments, the fused lipase CalB tagged with 6-histidine at the N terminal and 10-lysine at the C terminal (6His-CalB-10Lys) is effectively expressed with high solubility (0.

First Novozym 435 lipase-catalyzed Morita-Baylis-Hillman reaction in the presence of amides.

The first Novozym 435 lipase-catalyzed Morita-Baylis-Hillman (MBH) reaction with amides as co-catalyst was realized. Results showed that neither Novozym 435 nor amide can independently catalyze the reaction. This co-catalytic system that used a catalytic amount of Novozym 435 with a corresponding amount of amide was established and optimized.

Enzyme-Catalyzed Henry Reaction in Choline Chloride-Based Deep Eutectic Solvents.

The enzyme-catalyzed Henry reaction was realized using deep eutectic solvents (DESs) as a reaction medium. The lipase from Aspergillus niger (lipase AS) showed excellent catalytic activity toward the substrates aromatic aldehydes and nitromethane in choline chloride:glycerol at a molar ratio of 1:2. Addition of 30 vol% water to DES further improved the lipase activity and inhibited DES-catalyzed transformation.

Stereoselective synthesis of caffeic acid amides via enzyme-catalyzed asymmetric aminolysis reaction.

In this study, a new method was developed to prepare enantiopure caffeic acid amides by enzyme-catalyzed asymmetric aminolysis reaction. Methoxymethyl chloride (MOMCl) was first introduced as a protective and esterified reagent to obtain the MOM-protected caffeic acid MOM ester 1d. Aminolysis reaction occurred between 1d and (R, S)-α-phenylethylamine in the presence of an immobilized lipase (Novozym 435) from Candida antarctica.

Study on the enantioselectivity inhibition mechanism of acetyl-coenzyme A carboxylase toward haloxyfop by homology modeling and MM-PBSA analysis.

Acetyl-coenzyme A carboxylase (ACCase) has been identified as one of the most important targets of herbicide Aryloxyphenoxypropionates (APPs). ACCase shows different enantioselectivity toward APPs, and only (R)-enantiomers of APPs have the herbicidal activity. In order to deeply understand the enantioselective recognition mechanism of ACCase, (R)-haloxyfop, which is a typical commercial herbicide from APPs, is selected and the relative binding free energy between ACCase and (R)-haloxyfop is investigated and compared with that between ACCase and (S)-haloxyfop by homology modeling and molecular mechanics-Poisson-Boltzmann surface area (MM-PBSA) method.

Template enhanced activity of lipase accommodated in siliceous mesocellular foams.

Lipases were adsorbed in siliceous mesocellular foams containing different amounts of residual template in the nanopores. It is found that the hydrolytic activities of the adsorbed lipases are increased with increasing the contents of template in the mesopores. The triacetin hydrolytic activity of the lipase adsorbed in the foam containing 46% of template can be 13 times higher than that of the lipase adsorbed in the foam without template in the nanopores, and its specific activity is about three times higher than that of the free lipase, showing the hyperactivation effect on lipase resulting from the interaction between the lipase and the surfactant in the nanopores.