过程分析技术(PAT)在原料药生产中的应用

该文通过采用近红外光谱分析技术对原料药(API)的浓度调节过程进行实时监控,介绍了在良好生产规范条件下过程分析技术(PAT)的实施过程。利用偏最小二乘算法开发出两个校正模型分别用以监控原料药和水分含量,并通过模型校正均方根误差(RMSEC)、交叉检验均方根误差(RMSECV)和预测均方根误差(RMSEP)以及对应的决定系数(R~2)来评估模型的性能。为保证模型性能,按照分析方法验证要求对模型的线性和范围、准确性、精密度(重复性)、专属性以及稳健性指标进行验证。最后通过系统性能测试确认检测系统满足商业化运行的要求。结果显示,采用过程分析技术控制浓度调节过程,可以大幅度缩短浓度调节时间,节约蒸汽能耗和检测费用,减少生产过程中的偏差,提升产品工艺水平和批次间一致性。     

含有三苯胺-三唑双极性单元的橙红光阳离子型铱(Ⅲ)配合物的合成及在LEDs中的应用

以2-萘基吡啶(npy)为主配体, N,N-二苯基-4-[4-苯基-5-(吡啶-2-基)-4H-1,2,4-三唑-3-基]苯胺(DPPTA)为辅助配体, 合成了含有三苯胺-三唑双极性结构单元的橙红光阳离子型有机铱(Ⅲ)配合物[(npy)₂Ir(DPPTA)]PF₆. 该配合物的热分解温度高达345 ℃, 从20 ℃升温到100 ℃时, 相对发光强度衰减28.0%, 发光颜色稳定. 其所含的双极性结构单元使其能有效地吸收GaN芯片的蓝光(λ_em,max=455 nm), 进而可被蓝光高效激发. 以GaN蓝光芯片作为激发光源, [(npy)₂Ir(DPPTA)]PF₆为下转换发光材料, 可以制得橙红光LEDs; 进一步与黄光材料Y₃Al₅O₁₂∶Ce³⁺(YAG:Ce³⁺)联用, 可以制得高效的中性白光和暖白光LEDs.     

Crosslink-Enhanced Emission Effect on Luminescence in Polymers: Advances and Perspectives

The crosslink-enhanced emission effect was first proposed to explore the strong luminescence of nonconjugated polymer dots possessing only either non-emissive or weakly emissive sub-luminophores. Interesting phenomena in recent research indicate such enhancement caused by extensive crosslinking appears in diverse luminescent polymers with sub-luminophores (electron-rich heteroatomic moieties) or luminophores (conjugated π domains). This enhancement can promote the emission from nonluminous to luminous, from weakly luminous to strongly luminous, and even convert the pathway of radiative transitions. The concept of the crosslink-enhanced emission effect should be updated and extended to an in-depth spatial effect, such as electron overlap and energy splitting in confined domains by effective crosslinking, more than initial immobilization. This Minireview outlines the development of the crosslink-enhanced emission effect from the perspective of the detailed classification, inherent mechanism and applicable systems. An outlook on the further exploration and application of this theory are also proposed.     

Enzyme-Triggered Disassembly of Perylene Monoimide-based Nanoclusters for Activatable and Deep Photodynamic Therapy

Photodynamic therapy (PDT) exhibits great potential for cancer therapy, but still suffers from nonspecific photosensitivity and poor penetration of photosensitizer. Herein, a smart perylene monoimide-based nanocluster capable of enzyme-triggered disassembly is reported as an activatable and deeply penetrable photosensitizer. A novel carboxylesterase (CE)-responsive tetrachloroperylene monoimide (P1) was synthesized and assembled with folate-decorated albumins into a nanocluster ( FHP ) with a diameter of circa 100 nm. Once P1 is hydrolyzed by the tumor-specific CE, FHP disassembles into ultrasmall nanoparticles (ca. 10 nm), facilitating the deep tumor penetration of FHP . Furthermore, such enzyme-triggered disassembly of FHP leads to enhanced fluorescence intensity (ca. 8-fold) and elevated singlet oxygen generation ability (ca. 4-fold), enabling in situ near-infrared fluorescence imaging and promoted PDT. FHP permits remarkable tumor inhibition in vivo with minimal side effects through imaging-guided, activatable, and deep PDT. This work confirms that this cascaded multifunctional control through enzyme-triggered molecular disassembly is an effective strategy for precise cancer theranostics.     

Coal Pitch Derived Yellow-Emissive Carbon Dots and Their Application in Luminescent Solar Concentrators

Using coal pitch as the carbon source to synthesize carbon dots (CDs), one of the most promising photoluminescence (PL) materials, can play an important role in the global demand for carbon neutralization. However, the reported CDs derived from coal pitch are mainly limited blue emission. Here, a new route to synthesize yellow-emissive CDs from coal pitch is developed by extracting the lightweight aromatic compounds from coal pitch and solvothermally treating the extracts in dichloromethane in the presence of a small amount of nitric acid and sulfuric acid. Notably, the obtained CDs exhibit excitation independent yellow emission, large Stokes shift and good photostability. The application of the CDs for luminescent solar concentrators (LSCs) is evaluated. It is found that the CDs can be well dispersed in polymethyl methacrylate (PMMA) matrix and fabricated transparent LSCs. The synthesized LSC (4 × 4 × 0.2 cm³) with the optimal CDs concentration exhibits an optical conversion efficiency (η_opt) of 3.31% and power conversion efficiency (η_PCE) of 1.95% under simulated sun light illumination (100 mW cm⁻²). This research offers a new strategy to synthesize new kind of CDs with desired performance by exploiting the native chemistries of coal pitch.     

Selective extraction of palladium(II) using hydrazone ligand: A novel fluorescent sensor

The acyclic tridentate blue luminescent ligand (λ_ex=300 nm, λ_em=415 nm) quinoline-2-carboxaldehyde 2-pyridylhydrazone, HL, 1, was recognized as a new fluorescent chemosensor for Pd²⁺. In alkaline methanol complete fluorescent quenching was observed in the presence of 2 equivalents of Pd²⁺ that was further reflected in the solid phase fluorescence microscopic study.Ligand formed 1:1 complexes with Ni²⁺, Cu²⁺, Zn²⁺, Pd²⁺ and 1:2 complexes with Co²⁺, Fe²⁺ as obtained from Job's plot of continuous variation. The binding constants of different metal complexes (Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and Pd²⁺) were estimated by fluorescence titrations. The ligand can selectively extract significant amount of Pd²⁺ from the aqueous mixture of metal ions, and the extraction efficiency was increased from 80% to 95% with increase in the molar ratio of HL, 1, to Pd²⁺ from 1 to 3. No significant interference was observed up to 2-fold excess addition of Cu²⁺ and Zn²⁺ and 100-fold excess addition of Co²⁺, Fe²⁺ and Ni²⁺over the Pd²⁺ ion concentration (1.0×10⁻³ M).     

Syntheses,Crystal Structures and Luminescent Properties of a Dimeric Complex [(bzdmpzm)Cu(μ-I)]2 and a Polymeric Complex [(bzdmpzm)Cu(μ-NCS)]n (bzdmpzm=Bis(4-benzyl-3,5-dimethyl-1H-pyrazol-1-yl)methane)

Reactions of CuX (X=I, NCS) with bis(4‐benzyl‐3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methane (bzdmpzm) in MeCN resulted in the formation of one dimer [(bzdmpzm)Cu(µ‐I)]₂ ( 1 ) and one 1D polymer [(bzdmpzm)Cu(µ‐NCS)]_n ( 2 ) in high yields. 1 and 2 were characterized by elemental analysis, IR, ¹H NMR spectra, powder X‐ray diffraction and single‐crystal X‐ray diffraction. 1 consists of two scorpion‐like [(bzdmpzm)Cu]⁺ fragments bridged by two iodides, forming a dimeric structure. 2 contains a unique 1D scolopendra‐like chain of [(bzdmpzm)Cu]⁺ fragments linked by pairs of thiocyanates. The luminescence properties of 1 and 2 were also investigated.     

Single-Molecule White-Light-Emitting Starburst Donor-Acceptor Triphenylamine Derivatives and Their Application as Ratiometric Luminescent Molecular Thermometers

White-light emission (WLE) from a single molecule is a highly desirable alternative to a complex mixture of complementary colour emitters, which suffers from poor stability and reproducibility for potential use in organic electronic devices and lighting applications. We report single-molecule WLE both in solution and thin films by judiciously controlled π-electron delocalisation between the triarylamine subchromophoric units. Triphenylamine (TPA) forms the central core, and the phenyl rings are substituted with the electron-deficient acceptor 3-ethylrhodanine (Rh) and electron-rich donors triphenylamine or carbazole. The enforced biphenyl configuration of the TPA core and the other donors renders the π-conjugation across the entire chromophore poor, thus the individual subchromophoric units retain their individual emission characteristics, which cover all three primary colour emissions, that is, red, green and blue (RGB). TPA−Rh units exhibit broad fluorescence in the green-red region originating from the local excited (LE) state and intramolecular charge transfer state (ICT), strongly influenced by the solvent, water, and temperature. Different fluorescence parameters, including spectral maxima, ratiometric changes in ICT emission at the expense of blue emission from terminal donor units, and changes in lifetime, have a linear relationship with temperature between 180–330 K, thus the molecules can function as a multiparameter luminescent molecular thermometer. A temperature coefficient of 0.19 K⁻¹ in ratiometric fluorescence changes along with a spectral shift of 0.3 nm K⁻¹ and their workability over the wide temperature makes these molecules promising materials for potential applications. At lower temperatures, individual subchromophoric properties subside because of the reduced dihedral angle of biphenyl, and fluorescence from the whole molecule becomes dominant.     

Measuring the Sugar Content of Apples and Apple Juice by Near Infrared Spectroscopy

The sweetness of apples is usually measured by destructive inspection, which is time-consuming. As an alternative, a rapid instrument with high accuracy is very desirable. This paper reports an application using the NIR method to measure the sugar content of apples quantitatively. Samples containing mainly water showed that it was possible to measure the sugar content of fruit using the second derivative treatment (the background is removed) of the nearinfrared absorption spectrum. Measurements of the sugar content of four varieties of apples had correlation coefficients of 0.94 or more and a standard error of prediction (SEP) of 0.546°Bx at most. In the two kinds of apple juice, we obtained a SEP value of 0.439°Bx at most and correlation coefficients of 0.97 or more. We also found that 912 nm was an important wavelength for determining sugar content for both apples and juice. These results were in good agreement with calibrated values. NIR spectroscopy is a non-destructive measurement technique, and there is value in utilizing it for samples that are mainly water. Biotechnology applications are expected.     

Nanoparticle-doped Polymer Foils for Use in Solar Control Glazing

Since nanoparticles can provide spectrally selective absorption without scattering they can be used to dope polymers for use in windows, to provide a clear view while strongly attenuating both solar heat gain and UV, at lower cost than alternative technologies. The underlying physics and how it influences the choice and concentration of nanoparticle materials is outlined. Spectral data, visible and solar transmittance, and solar heat gain coefficient are measured for clear polymers and some laminated glass, in which the polymer layer is doped with conducting oxide nanoparticles. Simple models are shown to apply making general optical design straightforward. Use with clear glass and tinted glass is considered and performance shown to match existing solar control alternatives. A potential for widespread adoption in buildings and cars is clearly demonstrated, and scopes for further improvements are identified, so that ultimately both cost and performance are superior.