Comparative Analysis of Tenecteplase versus Alteplase in Acute Ischemic Stroke: A Multicentric Observational Study from Eastern India.

BACKGROUND: Tenecteplase is used as an alternative to alteplase and is considered noninferior for thrombolysis in acute ischemic stroke. OBJECTIVES: To compare the effectiveness and adverse effects of tenecteplase and alteplase in the real-world management of acute ischemic stroke. MATERIALS AND METHODS: In this retrospective observational study, we collected data from acute ischemic stroke patients admitted in six hospitals in West Bengal, India, and were thrombolysed with tenecteplase or alteplase between July 2021 and June 2022. Demographic data, baseline parameters, hospital course, and 3-month follow-up data were collected. The percentage of patients achieving a score of 0-2 in the modified Ranking scale at 3 months, rate of symptomatic intracranial hemorrhage, and all-cause mortality within 3 months were the main parameters of comparison between the two thrombolytic agents. RESULTS: A total of 162 patients were initially included in this study. Eight patients were excluded due to unavailability of follow-up data. Among the remaining patients, 71 patients received tenecteplase and 83 patients received alteplase. There was no statistically significant difference between tenecteplase and alteplase with respect to the percentage of patients achieving functional independence (modified Rankin scale score 0-2) at 3 months (53.5% vs. 60.2%, P = 0.706), rate of symptomatic intracranial hemorrhage (5.6% vs. 10.8%, P = 0.246), and all-cause mortality at 3 months (11.3% vs. 15.7%, P = 0.628). CONCLUSION: The effectiveness of tenecteplase is comparable to alteplase in the real-world management of acute ischemic stroke. Symptomatic intracranial hemorrhage and all-cause mortality rates are also similar in real-world practice.

Acid-induced nitrite reduction of nonheme iron(ii)-nitrite: mimicking biological Fe-NiR reactions.

Nitrite reductase (NiR) catalyzes nitrite (NO2 -) to nitric oxide (NO) transformation in the presence of an acid (H+ ions/pH) and serves as a critical step in NO biosynthesis. In addition to the NiR enzyme, NO synthases (NOSs) participate in NO production. The chemistry involved in the catalytic reduction of NO2 -, in the presence of H+, generates NO with a H2O molecule utilizing two H+ + one electron from cytochromes and is believed to be affected by the pH. Here, to understand the effect of H+ ions on NO2 - reduction, we report the acid-induced NO2 - reduction chemistry of a nonheme FeII-nitrito complex, [(12TMC)FeII(NO2 -)]+ (FeII-NO2 -, 2), with variable amounts of H+. FeII-NO2 - upon reaction with one-equiv. of acid (H+) generates [(12TMC)Fe(NO)]2+, {FeNO}7 (3) with H2O2 rather than H2O. However, the amount of H2O2 decreases with increasing equivalents of H+ and entirely disappears when H+ reaches ≅ two-equiv. and shows H2O formation. Furthermore, we have spectroscopically characterized and followed the formation of H2O2 (H+ = one-equiv.) and H2O (H+ ≅ two-equiv.) and explained why bio-driven NiR reactions end with NO and H2O. Mechanistic investigations, using 15N-labeled-15NO2 - and 2H-labeled-CF3SO3D (D+ source), revealed that the N atom in the {Fe14/15NO}7 is derived from the NO2 - ligand and the H atom in H2O or H2O2 is derived from the H+ source, respectively.

Exploring the nitric oxide dioxygenation (NOD) reactions of manganese-peroxo complexes.

Here, we report the nitric oxide dioxygenation (NOD) reactions of two MnIII-peroxo (MIII-O22-) complexes, [(3PYENMe)MnIII(O22-)]+ (1) and [(N3PY)MnIII(O22-)]+ (2), bearing pentadentate ligands. Complexes 1 and 2 give MnII-nitrate (MnII-NO3-) complexes (3 and 4) when reacted with nitric oxide (NO), respectively. The mechanistic study explored by using 2,4-di-tert-butylphenol (2,4-DTBP) suggested that the NOD reaction of 1 and 2 occurs via a presumed Mn-peroxynitrite ([Mn-PN]+, [Mn-ONOO-]+) intermediate. Tracking the source of N atoms using 15NO revealed that the N-atoms in MnII-NO3- (3 and 4) are derived from the 15NO moiety. Furthermore, we have explored the MIII-O22- regeneration from NOD products (3 and 4), and we have observed the formation of MIII-O22- complexes (1 and 2) upon treatment with KO2 or H2O2/triethylamine (TEA), respectively.

Itraconazole Confers Cytoprotection Against Neurodegenerative Disease-Associated Abnormal Protein Aggregation.

Cells perform regular maintenance to avoid the accumulation of misfolded proteins. Prolonged accumulation of these proteotoxic inclusions generates potential risk of ageing-related diseases such as neurodegenerative diseases. Therefore, removal of such abnormal aggregates can ensure the re-establishment of proteostasis. Ubiquitin proteasome system (UPS) actively participates in the selective removal of aberrantly folded clients with the help of complex proteasome machinery. However, specific induction of proteasome functions to remove abnormal proteins remains an open challenge. Here, we show that Itraconazole treatment induces proteasome activities and degrades the accumulation of bonafide-misfolded proteins, including heat-denatured luciferase. Exposure of Itraconazole elevates the degradation of neurodegenerative disease-associated proteins, e.g. expanded polyglutamine, mutant SOD1, and mutant α-synuclein. Our results suggest that Itraconazole treatment prevents the accumulation of neurodegenerative disease-linked misfolded proteins and generates cytoprotection. These findings reveal that Itraconazole removes abnormal proteins through sequential proteasomal activation and represents a potential protective therapeutic role against protein-misfolding neurodegenerative diseases.

Exceptional-point-induced asymmetric mode conversion in a dual-core optical fiber segment.

The engineering of exceptional points (EPs) in open optical systems has lately attracted much attention for developing future all-optical devices. However, investigation of the fascinating features of EPs in fiber geometries is lacking. We design a fabrication feasible dual-core optical fiber segment, where non-Hermiticity in terms of a symmetric customized gain-loss profile is introduced to modulate the interaction between two corresponding coupled modes toward hosting a dynamical EP encirclement scheme in the gain-loss parameter space. An asymmetric conversion process between two supported modes is reported by exploiting the chirality of the encountered EP. The proposed scheme can lead to an advanced platform to design mode-manipulative all-optical components in communication and all-fiber photonic devices.

Why intermolecular nitric oxide (NO) transfer? Exploring the factors and mechanistic aspects of NO transfer reaction.

Small molecule activation and their transfer reactions in biological or catalytic reactions are greatly influenced by the metal-centers and the ligand frameworks. Here, we report the metal-directed nitric oxide (NO) transfer chemistry in low-spin mononuclear {Co(NO)}8, [(12-TMC)CoIII(NO-)]2+ (1-CoNO, S = 0), and {Cr(NO)}5, ([(BPMEN)Cr(NO)(Cl)]+) (4-CrNO, S = 1/2) complexes. 1-CoNO transfers its bound NO moiety to a high-spin [(BPMEN)CrII(Cl2)] (2-Cr, S = 2) and generates 4-CrNOvia an associative pathway; however, we did not observe the reverse reaction, i.e., NO transfer from 4-CrNO to low-spin [(12-TMC)CoII]2+ (3-Co, S = 1/2). Spectral titration for NO transfer reaction between 1-CoNO and 2-Cr confirmed 1 : 1 reaction stoichiometry. The NO transfer rate was found to be independent of 2-Cr, suggesting the presence of an intermediate species, which was further supported experimentally and theoretically. The experimental and theoretical observations support the formation of µ-NO bridged intermediate species ({Cr-NO-Co}4+). Mechanistic investigations using 15N-labeled-15NO and tracking the 15N-atom established that the NO moiety in 4-CrNO is derived from 1-CoNO. Further, to investigate the factors deciding the NO transfer reactivity, we explored the NO transfer reaction between another high-spin CrII-complex, [(12-TMC)CrII(Cl)]+ (5-Cr, S = 2), and 1-CoNO, showing the generation of the low-spin [(12-TMC)Cr(NO)(Cl)]+ (6-CrNO, S = 1/2); however, again there was no opposite reaction, i.e., from Cr-center to Co-center. The above results advocate clearly that the NO transfer from Co-center generates thermally stable and low-spin and inert {Cr(NO)}5 complexes (4-CrNO & 6-CrNO) from high-spin and labile Cr-complexes (2-Cr & 5-Cr), suggesting a metal-directed NO transfer (cobalt to chromium, not chromium to cobalt). These results explicitly highlight that the NO transfer is strongly influenced by the labile/inert behavior of the metal-centers and/or thermal stability rather than the ligand architecture.

Baseline Optical Coherence Tomography Parameters That May Influence 6 Months Treatment Outcome of Polypoidal Choroidal Vasculopathy Eyes with Combination Therapy: A Short-Term Pilot Study.

Although optical coherence tomography (OCT) parameters have assisted in the diagnosis of polypoidal choroidal vasculopathy (PCV), its potential to evaluate treatment outcomes has not been established. The purpose of this pilot study was to evaluate baseline OCT parameters that may influence treatment outcome in PCV eyes with combination therapy. In this single-centered, prospective study, patients were recruited with at least one treatment-naïve PCV eye and treated with combination therapy of intravitreal anti-vascular endothelial growth factor and photodynamic therapy. Best-corrected distance and near visual acuity (DVA and NVA), and contrast sensitivity (CS) were recorded at baseline and six months after treatment. OCT parameters were determined. Twenty-six eyes of 26 patients aged between 51 to 83 years were evaluated. In eyes that had disrupted external limiting membrane (ELM), photoreceptors inner and outer segment (IS-OS) junction at 1000 micron of fovea at baseline showed low mean visual functions after 6 months of treatment. Eyes with foveal sub-retinal fluid (SRF) and polyp at central 1000 micron of fovea at baseline showed significantly worse DVA and CS after six months. Thus, the presence of foveal SRF, foveal polyp, disrupted ELM, and IS-OS junction at baseline significantly influenced the six months' visual outcome in PCV eyes treated with combination therapy.

Visual Parameters and Retinal Morphology for Polypoidal Choroidal Vasculopathy Pre- and Post-Intravitreal Ranibizumab with or without Photodynamic Therapy: A Short-Term Prospective Study.

The objective of this study was to compare visual parameters and retinal layers' morphology pre-treatment (baseline) and 6 months post-treatment in polypoidal choroidal vasculopathy (PCV) eyes. A single centre, longitudinal, prospective study was conducted at a public tertiary hospital of Malaysia. Visual parameters including distance and near visual acuity (DVA and NVA), contrast sensitivity (CS), reading speed (RS), and different qualitative and quantitative optical coherence tomography (OCT) parameters were evaluated pre- and 6 months post-treatment. Thirty-three naïve PCV eyes of 32 patients (mean age of 67.62 years) were evaluated pre- and post-treatment of intravitreal ranibizumab with and without photodynamic therapy. After treatment, sub retinal fluid decreased from 27 eyes (84.35%) at baseline to 7 eyes (21.88%) at 6 months while pigment epithelium detachment decreased from 32 eyes (100%) at base line to 15 eyes (46.87%) at 6 months. Mean pre-treatment quantitative morphological OCT retinal parameters including thickness and volume of central sub field, center thickness, center minimum, and maximum thickness reduced significantly. Similarly, all visual parameters including DVA, NVA, CS, and RS showed statistically significant improvement. While 89% of the eyes showed improvement in CS, 78%, 71%, and 65% of the eyes showed improvement in NVA, RS, and DVA, respectively. Thus, CS was the most treatment responsive visual parameter.

On-Board Ship Detection for Medium Resolution Optical Sensors.

In recent years there has been an increased interest in ocean surveillance. The activity includes control and monitoring of illegal fisheries, manmade ocean pollution and illegal sea traffic surveillance, etc. The key problem is how to identify ships and ship-like objects accurately and in a timely manner. In this context, currently, many solutions have been proposed based on high resolution optical and radar remote sensing systems. Most often, these systems suffer from two major limitations viz., limited swath, thereby requiring multiple satellites to cover the region of interest and huge volumes of data being transmitted to ground, even though effective per-pixel information content is minimal. Another limitation is that the existing systems are either simulated on ground or built using the non-space qualified/Commercial Of-The-Shelf (COTS) components. This paper proposes an efficient on-board ship detection system/package connected with medium resolution wide swath optical camera. The methodology adopted has three major components, viz., onboard data processing for improving the radiometric fidelity, followed by a ship detection using modified Constant False Alarm Rate algorithm (CFAR) and a false alarm suppression module to mask false identifications. Finally, the package outputs only the locations of the ships, which is transmitted to the ground. The proposed system reduces the effective volume of data to be transmitted and processed on ground and also significantly cuts down the turnaround time for achieving the end objective. The system is built on radiation hardened Field Programmable Gate Array (FPGA) devices to meet the various engineering constraints such as real-time performance, limited onboard power, radiation hardness, handling of multiple custom interfaces etc. The system is tested with one of the medium resolution Multispectral Visual and Near Infra-Red (MX-VNIR) sensor having a spatial resolution of around 50 m and swath of around 500 Kms, which would be flown with one of the upcoming satellites. The systems performance is also verified on ground with Indian Remote Sensing (IRS) Satellite's Resourcesat's Advanced Wide Field Sensor (AWiFS) data and the results are found to be quite encouraging as well as meeting the mission objectives.

Activation of DNA damage response signaling in mammalian cells by ionizing radiation.

Cellular responses to DNA damage are fundamental to preserve genomic integrity during various endogenous and exogenous stresses. Following radiation therapy and chemotherapy, this DNA damage response (DDR) also determines development of carcinogenesis and therapeutic outcome. In humans, DNA damage activates a robust network of signal transduction cascades, driven primarily through phosphorylation events. These responses primarily involve two key non-redundant signal transducing proteins of phosphatidylinositol 3-kinase-like (PIKK) family - ATR and ATM, and their downstream kinases (hChk1 and hChk2). They further phosphorylate effectors proteins such as p53, Cdc25A and Cdc25C which function either to activate the DNA damage checkpoints and cell death mechanisms, or DNA repair pathways. Identification of molecular pathways that determine signaling after DNA damage and trigger DNA repair in response to differing types of DNA lesions allows for a far better understanding of the consequences of radiation and chemotherapy on normal and tumor cells. Here we highlight the network of DNA damage response pathways that are activated after treatment with different types of radiation. Further, we discuss regulation of cell cycle checkpoint and DNA repair processes in the context of DDR in response to radiation.

A MULTISCALE VISION-ILLUSTRATIVE APPLICATIONS FROM BIOLOGY TO ENGINEERING.

Modeling and simulation have quickly become equivalent pillars of research along with traditional theory and experimentation. The growing realization that most complex phenomena of interest span many orders of spatial and temporal scales has led to an exponential rise in the development and application of multiscale modeling and simulation over the past two decades. In this perspective, the associate editors of the International Journal for Multiscale Computational Engineering and their co-workers illustrate current applications in their respective fields spanning biomolecular structure and dynamics, civil engineering and materials science, computational mechanics, aerospace and mechanical engineering, and more. Such applications are highly tailored, exploit the latest and ever-evolving advances in both computer hardware and software, and contribute significantly to science, technology, and medical challenges in the 21st century.

Oxygen atom transfer promoted nitrate to nitric oxide transformation: a step-wise reduction of nitrate → nitrite → nitric oxide.

Nitrate reductases (NRs) are molybdoenzymes that reduce nitrate (NO3 -) to nitrite (NO2 -) in both mammals and plants. In mammals, the salival microbes take part in the generation of the NO2 - from NO3 -, which further produces nitric oxide (NO) either in acid-induced NO2 - reduction or in the presence of nitrite reductases (NiRs). Here, we report a new approach of VCl3 (V3+ ion source) induced step-wise reduction of NO3 - in a CoII-nitrato complex, [(12-TMC)CoII(NO3 -)]+ (2,{CoII-NO3 -}), to a CoIII-nitrosyl complex, [(12-TMC)CoIII(NO)]2+ (4,{CoNO}8), bearing an N-tetramethylated cyclam (TMC) ligand. The VCl3 inspired reduction of NO3 - to NO is believed to occur in two consecutive oxygen atom transfer (OAT) reactions, i.e., OAT-1 = NO3 - → NO2 - (r1) and OAT-2 = NO2 - → NO (r2). In these OAT reactions, VCl3 functions as an O-atom abstracting species, and the reaction of 2 with VCl3 produces a CoIII-nitrosyl ({CoNO}8) with VV-Oxo ({VV[double bond, length as m-dash]O}3+) species, via a proposed CoII-nitrito (3, {CoII-NO2 -}) intermediate species. Further, in a separate experiment, we explored the reaction of isolated complex 3 with VCl3, which showed the generation of 4 with VV-Oxo, validating our proposed reaction sequences of OAT reactions. We ensured and characterized 3 using VCl3 as a limiting reagent, as the second-order rate constant of OAT-2 (k 2 /) is found to be ∼1420 times faster than that of the OAT-1 (k 2) reaction. Binding constant (K b) calculations also support our proposition of NO3 - to NO transformation in two successive OAT reactions, as K b(CoII-NO2 -) is higher than K b(CoII-NO3 -), hence the reaction moves in the forward direction (OAT-1). However, K b(CoII-NO2 -) is comparable to K b{CoNO}8 , and therefore sequenced the second OAT reaction (OAT-2). Mechanistic investigations of these reactions using 15N-labeled-15NO3 - and 15NO2 - revealed that the N-atom in the {CoNO}8 is derived from NO3 - ligand. This work highlights the first-ever report of VCl3 induced step-wise NO3 - reduction (NRs activity) followed by the OAT induced NO2 - reduction and then the generation of Co-nitrosyl species {CoNO}8.

Patient-Perceived Benefit of Treatment in Polypoidal Choroidal Vasculopathy: A Pilot Study.

Polypoidal choroidal vasculopathy (PCV), a subtype of neovascular age-related macular degeneration, requires repeated treatment. The objective of this pilot study was to evaluate and compare vision-targeted quality of life (QOL) at baseline and after 6 months of treatment in patients with PCV. Naive PCV patients were recruited. Visual functions assessed were distance visual acuity (DVA), near visual acuity (NVA), contrast sensitivity (CS), reading speed (RS), and QOL at baseline and after 6 months of treatment. Thirty patients (average age of 67.62 ± 8.05 years) revealed mean DVA and NVA improvements of 0.24 logMAR and 0.30 logMAR, respectively. Mean CS and RS improved by 0.39 log contrast and 25.58 words per minute, respectively. The National Eye Institute Visual Function Questionnaire 25 (NEI-VFQ-25) composite score significantly increased from a baseline of 66.73 ± 13.74 to 73.54 ± 14.26. Twenty-eight of the patients showed overall improvement in QOL score by 5 units or more or remained stable. Subscales of NEI-VFQ-25 significantly improved, with general vision, mental health, and role difficulties improving by 10 or more units. The present pilot study reports a significant improvement of QOL in PCV patients after 6 months of treatment, with mental health, role difficulties, social functioning, and distance vision activities being the most improved subscales.

Correlation between Visual Functions and Retinal Morphology in Eyes with Early and Intermediate Age-Related Macular Degeneration.

In early and intermediate age related macular degeneration (ARMD), visual acuity alone has failed to explain the complete variation of vision. The aim of the present study was to determine correlation between different visual functions and retinal morphology in eyes with early and intermediate ARMD. In this single center cross sectional study, patients diagnosed as early or intermediate ARMD in at least one eye were recruited. Visual functions measured were best- corrected distance visual acuity (DVA), near vision acuity (NVA), reading speed (RS), and contrast sensitivity (CS). Parameters such as thickness (RT) and volume (RV) of the retina, outer retinal layer thickness (ORLT) and volume (ORLV), outer nuclear layer thickness (ONLT) and volume (ONLV), retinal pigment epithelium layer-Bruch's membrane complex thickness (RPET) and volume (RPEV) were assessed employing semi-auto segmentation method of Spectralis optical coherence tomography (OCT). Twenty-six eyes were evaluated. DVA, CS, and RS showed significantly good correlation with RPET, ONLT, and ONLV, whereas NVA showed good correlation with ONLV and RPET. The present study concluded that RS, CS, NVA, and DVA represent the morphological alteration in early stages and should be tested in clinical settings. ONLT, ONLV, and RPET morphological parameters can be employed as important biomarkers in diagnosis of early to intermediate ARMD.

Fumaric acid incorporated Ag/agar-agar hybrid hydrogel: A multifunctional avenue to tackle wound healing.

Wound and its treatment is one of the major health concerns throughout the globe. Various extrinsic and intrinsic factors can influence the dynamics of healing mechanism. One such extrinsic factor is moist environment in wound healing. The advantages of optimum hydration in wound healing are enhanced autolytic debridement, angiogenesis and accelerated cell proliferation and collagen formation. But hydrated wounds often end up with patient's uncomfortability, associated infection, and tissue lipid peroxidation. Healing process prefers antimicrobial, anti-inflammatory and optimum moist microenvironment. Here, we have synthesized fumaric acid incorporated agar-silver hydrogel (AA-Ag-FA); characterized by UV-Visible spectroscopy, FTIR spectroscopy and TEM. The surface morphology is evaluated through SEM. The size of the silver nanoparticles (Ag NPs) was found to be 10-15 nm. The hydrogel shows potential antibacterial effect against Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa which are predominantly responsible for wound infection. The gel shows reasonable antioxidant property evaluated through 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. Topical application of the gel on the wound site heals the wound at much faster rate even compared to standard (Mega heal, Composition: Colloidal silver 32 ppm hydrogel) gel. Histological analysis reveals better tissue proliferation (i.e. epithelialization), more granulation tissue formation, neovascularisation, fibroblast and mature collagen bundles. The lipid peroxidation of wound tissue estimated through malondialdehyde (MDA) assay was found to be reasonably less when treated with AA-Ag-FA hydrogel compared to standard (Mega heal). Cytotoxicity of the samples tested through MTT assay and live-dead cell staining shows its nontoxic biocompatibility nature. In our hydrogel scaffold, the bio-degradable agar-agar provides the moist environment; the Ag NPs inside the gel acts as bactericidal agent and fumaric acid facilities the antioxidant and angiogenesis path implicitly.

Chirality breakdown in the presence of multiple exceptional points and specific mode excitation.

The dynamical parametric encirclement around a second-order exceptional point (EP) enables the time-asymmetric nonadiabatic evolution of light, which follows the chirality of the underlying system. Such light dynamics in the presence of multiple EPs and the corresponding chiral aspect is yet to be explored. In this Letter, we report a gain-loss assisted four-mode-supported optical waveguide that hosts a parameter space to dynamically encircle multiple EPs. In the presence of multiple EPs, we establish a unique nonadiabatic behavior of light, where beyond the chiral aspect of the system, light is switched to a particular mode, irrespective of the choice of the input mode. Proposed scheme certainly opens a step-forward approach in light manipulation to facilitate next-generation integrated photonic systems.

Nitric oxide monooxygenation (NOM) reaction of cobalt-nitrosyl {Co(NO)}8 to CoII-nitrito {CoII(NO2 -)}: base induced hydrogen gas (H2) evolution.

Here, we report the nitric oxide monooxygenation (NOM) reactions of a CoIII-nitrosyl complex (1, {Co-NO}8) in the presence of mono-oxygen reactive species, i.e., a base (OH-, tetrabutylammonium hydroxide (TBAOH) or NaOH/15-crown-5), an oxide (O2- or Na2O/15-crown-5) and water (H2O). The reaction of 1 with OH- produces a CoII-nitrito complex {3, (CoII-NO2 -)} and hydrogen gas (H2), via the formation of a putative N-bound Co-nitrous acid intermediate (2, {Co-NOOH}+). The homolytic cleavage of the O-H bond of proposed [Co-NOOH]+ releases H2 via a presumed CoIII-H intermediate. In another reaction, 1 generates CoII-NO2 - when reacted with O2- via an expected CoI-nitro (4) intermediate. However, complex 1 is found to be unreactive towards H2O. Mechanistic investigations using 15N-labeled-15NO and 2H-labeled-NaO2H (NaOD) evidently revealed that the N-atom in CoII-NO2 - and the H-atom in H2 gas are derived from the nitrosyl ligand and OH- moiety, respectively.

A Droplet-Based Microfluidics Route to Temperature-Responsive Colloidal Molecules.

Small clusters of spherical colloids that mimic real molecules, so-called colloidal molecules, hold great promise as building blocks in bottom-up routes to new materials. However, their typical hard sphere nature has hampered their assembly into ordered structures, largely due to a lack of control in the interparticle interactions. To provide easy external control of the interactions, the present work focuses on the preparation of colloidal molecules from temperature-responsive microgel particles that undergo a transition from a soft repulsive to a short-range attractive state as their characteristic volume phase transition temperature (VPTT) is crossed. Preparation of the colloidal molecules starts with the use of a droplet-based microfluidics device to form highly uniform water-in-oil (W/O) emulsion droplets containing, on average and with a narrow distribution, four microgels per droplet. Evaporation of the water then leads to the formation of colloidal molecule-like clusters, which can be harvested following cross-linking and phase transfer. We use a mixture of two types of microgels, one based on poly(N-isopropylacrylamide) (PNIPAM) and the other on poly(N-isopropylmethacrylamide) (PNIPMAM), to prepare bicomponent colloidal molecules, and show that the difference in VPTT between the two allows for induction of attractive interparticle interactions between the PNIPAM interaction sites at temperatures in between the two VPTTs, analogous to the interactions among patchy biomacromolecules such as many proteins.

Finding a new pathway for acid-induced nitrite reduction reaction: formation of nitric oxide with hydrogen peroxide.

Here, we report a new pathway for nitrite reduction chemistry, formation of cobalt-nitrosyl ({CoII-NO}8) with H2O2 in the reaction of a CoII-nitrito complex with a one-fold acid (H+) via the formation of a CoII-nitrous acid intermediate ({CoII-ONOH}). Mechanistic investigations using 15N-labeled-15NO2- revealed that the N-atom in the {CoII-NO}8 complex is derived from the nitrito ligand, and H2O2 came from the homolysis of the ON-OH moiety. Spectral evidence supporting the formation of the CoII-ONOH intermediate and the generation of H2O2 is also presented.

Asymmetric propagation and limited wavelength translation of optical pulses through a linear dispersive time-dynamic system.

We study optical pulse propagation through a linear, dispersive, gain-loss-assisted bulk medium whose refractive index is time-varying. To analyze the dynamics, we have used a novel technique of time transformation that provides universal formulas of pulse propagation. Our analytical and numerical investigations reveal that optical pulses show asymmetric behavior while propagating in opposite direction through such a medium, in both the temporal and spectral domains. Moreover, the wavelength shift during this process is the most interesting outcome which is limited in range, but could be tuned by varying the refractive index with time. Phenomena that are observed in this Letter are novel and realizable in practical devices such as coupled waveguides where the refractive index is a function of time.